Complexation With Aminopolycarboxylic Acids

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Electronic Theses, Treatises and Dissertations
The Graduate School
4-9-2004
Complexation of f-Elements with

Aminopolycarboxylate Ligands
Glenn A. Fugate
Florida State University
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Fugate, Glenn A., "Complexation of f-Elements with Aminopolycarboxylate Ligands" (2004). Electronic Theses, Treatises and
Dissertations. Paper 4387.
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THE FLORIDA STATE UNIVERSITY

COLLEGE OF ARTS AND SCIENCES
COMPLEXATION OF f-ELEMENTS WITH

AMINOPOLYCARBOXYLATE LIGANDS
By
GLENN A. FUGATE
A Dissertation submitted to the

Department of Chemistry
in partial fulfillment of the
requirements for the degree of
Doctor of Philosophy
Degree Awarded:
Spring Semester, 2004
The members of the Committee approve the dissertation of Glenn A. Fugate defended on
9 April 2004.
__________________________
Gregory R. Choppin
Professor Directing Dissertation
__________________________
William M. Landing
Outside Committee Member
__________________________
Naresh Dalal
Committee Member
__________________________
Kenneth A. Goldsby
Committee Member
The Office of Graduate Studies has verified and approved the above named
committee members.
ii
ACKNOWLEDGEMENTS
I would like to thank my major professor, Dr. Gregory R. Choppin, for his
patience, aid and guidance throughout this project.
I would like to thank Dr. Kenneth L. Nash of Argonne National Laboratory for
past, present and future guidance, for his help and ideas on this project and for being my
friend.
I would like to thank all the past and present members of the Choppin group for
their help, guidance and camaraderie. I would like especially like to thank: Dr. Craig
Van Pelt, Dr. Michael G. Bronkowski and Dr. William J. Crooks for help getting started
in the laboratory, Dr. Serguei I. Sinkov for his help and insight, Dr. Ivan Laszak, Dr.
Isabel Paiva and Dr. Clara Comuzzi for their friendship, Dr. Alfred Morgenstern for
helping me leave the laboratory more often, and Dr. Marian Borkowski for games of
pool, knowledge, support and friendship.
I appreciate help I have received from staff members of the Department of
Chemistry. I would especially like to thank: Dr. David Gorman and Dr. Burt van de
Burrgt for their help with laser fluorescence experiments and equipment, Dr. Ronald J
Clark for determining the crystal structures in this work, Dave Parker, Charlie Betts, Gary
Poplin and Tom Wages for help with electronic and computer problems, Randall Pelt for
making glass replacement parts quickly, Lamar Norman and Keith Collins for help in
repairing mechanical problems, and Dr. Joseph B. Vaughn, Steve Freitag and Dr. Thomas
Gedris for help with the setup and operation of the NMR experiments in this work. Dr.
Gedris is due additional thanks for running some of the NMR spectra as well as being a
great gardener, an excellent cue maker, a fantastic pool player and teacher and a generally
remarkable human being.
iii
I would like to thank Dr. Paul Rickert of Argonne National Laboratory for the
synthesis of two of the ligands studied in the work.
I would like to thank the friends who have helped me through this process: Dr.
Joseph Lehnes for his love of football, video games and late night dinners, Dr. Jennifer
Llewelyn for being a good listener, Dr. Elizabeth Libby Mayo, Amy Aldridge, David
Gilmore, Dr. David Sunseri, Doug Hattaway, Dr. Thomas Gedris, Dr. Marian Borkowski
and all the other members of The Village Idiots for a lot of laughs during a little pool.
Lastly, I would like to thank my family for their help, love, support and
understanding.
iv
TABLE OF CONTENTS
List of Tables
................................................................................................ix
List of Figures
................................................................................................xi
List of Abbreviations and Symbols ....................................................................xii
Abstract
......................................................................................................xiii
1. INTRODUCTION ..........................................................................................1
1.1 Statement of Problem............................................................................1
1.2 Aminocarboxylate Properties................................................................2
1.3 Lanthanide(III) Elements ......................................................................3
1.3.1 General Properties........................................................................3
1.3.2 Comparison of Lanthanide Ions (4f) with Actinide Ions (5f) ......4
1.3.3 Separation of Lanthanide(III) and Actinide(III) Ions ..................4
1.3.4 Spectroscopy of Lanthanides .......................................................5
1.4 Objectives of Present Work ..................................................................6
2. EXPERIMENTAL..........................................................................................14
2.1 Chemical Reagents................................................................................14
2.1.1 Lanthanide(III) Perchlorate Stock Solutions ...............................14
2.1.2 Sodium Perchlorate Stock Solutions............................................15
2.1.3 Ligands.........................................................................................15
2.1.3.1 Chelidamic Acid ..............................................................15
2.1.3.2 Piperidine-2,6-dicarboxylic Acid.....................................15
2.1.3.3 2,6-Dicarboxypipepridine-N-acetic Acid ........................16
2.1.4 Potentiometric Titration Solutions...............................................16
2.1.4.1 Sodium Hydroxide Standard Solutions............................16
2.1.4.2 Perchloric Acid Standard Solutions .................................16
2.1.4.3 Ligand Solutions ..............................................................17
2.1.4.4 Lanthanide(III) Complex Solutions .................................17
2.1.5 Laser Induced Fluorescence Solutions.........................................17
2.1.6 Hypersensitivity Spectroscopy Solutions ....................................18
2.1.7 Nuclear Magnetic Resonance Solutions ......................................18
2.1.7.1 Solutions for Adjusting pH ..............................................18
v
2.1.7.2 Ligands Solutions.............................................................19

2.1.7.3 Lanthanide(III) Complex Solutions .................................19
2.1.8 Crystals ........................................................................................20
2.1.9 Calorimetry Solutions ..................................................................20
2.1.9.1 Standard Solutions ...........................................................20
2.1.9.2 Ligand Solutions ..............................................................20
2.1.9.3 Lanthanide(III) Perchlorate Solutions..............................21
2.2 Equipment .............................................................................................21
2.2.1 Mass Determination .....................................................................21
2.2.2 Potentiometric Measurements......................................................21
2.2.3 Potentiometric Titrations .............................................................21
2.2.4 Laser Induced Fluorescence.........................................................22
2.2.4.1 Fluorescence Spectra .......................................................22
2.2.4.2 Fluorescence Lifetime Measurements .............................23
2.2.5 Hypersensitivity Spectroscopy.....................................................23
2.2.6 NMR ............................................................................................23
2.2.7 Crystallography............................................................................24
2.2.8 Calorimetry ..................................................................................24
2.3 Procedures.............................................................................................25
2.3.1 Potentiometric Measurements......................................................25
2.3.2 Potentiometric Titrations .............................................................25
2.3.2.1 Standardization ................................................................25
2.3.2.2 Acid Dissociation Constant Determination .....................26
2.3.2.3 Stability Constant Determination.....................................26
2.3.3 Laser Induced Fluorescence.........................................................26
2.3.3.1 Fluorescence Experiments ...............................................26
2.3.3.2 Fluorescence Lifetime Experiments ................................27
2.3.4 Hypersensitivity Spectroscopy.....................................................27
2.3.5 NMR ............................................................................................27
2.3.5.1 pH Titrations ....................................................................27
2.3.5.2 Coalescence Experiments ................................................28
2.3.5.3 Nuclear Overhauser Effect Experiments .........................28
2.3.5.4 13C 1H Decoupled Spectra................................................29
2.3.5.5 1H Homonuclear Decoupled Spectra ...............................29
2.3.6 Crystallography............................................................................29
2.3.7 Calorimetry ..................................................................................30
2.3.7.1 Heat of Dilution ...............................................................30
2.3.7.2 Standardization ................................................................31
2.3.7.3 Heat of Protonation ..........................................................31
2.3.7.4 Heat of Complexation ......................................................31
3. CALCULATIONS..........................................................................................32
3.1 Potentiometric Titrations ......................................................................32
3.1.1 Electrode Calibration ...................................................................32
3.1.2 Acid Dissociation Constant Determination .................................33
vi
3.1.3 Lanthanide(III) Complex Stability Constant Determination .......34

3.2 PSEQUAD ............................................................................................34
3.3 Laser Induced Fluorescence..................................................................35
3.3.1 Fluorescence Lifetime Measurements .........................................35
3.3.2 Fluorescence Spectra ...................................................................35
3.4 Hypersensitivity Spectroscopy..............................................................36
3.5 NMR ................................................................................................37
2.5.2 Nuclear Overhauser Effect...........................................................39
3.6 Calorimetry ...........................................................................................40
3.6.1 Change of Enthalpy......................................................................40
3.6.2 Change of Entropy .......................................................................41
4. RESULTS. ..............................................................................................42
4.1 Acid Dissociation Constants .................................................................42
4.2 Lanthanide(III) Stability Constants.......................................................43
4.3 Calorimetry ...........................................................................................43
4.4.1 PDA..............................................................................................44
4.4.2 DPA and CA ................................................................................44
4.4.3 Oscillator Strengths......................................................................46
4.5 Eu(III) Laser Fluorescence ...................................................................46
4.5.1 Excitation Spectra ........................................................................46
4.5.2 PDA..............................................................................................47
4.5.3 DPA..............................................................................................47
4.5.4 CA ................................................................................................48
4.6 NMR ................................................................................................49
4.6.2 1H NMR Peak Identification of PDA ..........................................49
4.6.3 1H NMR Peak Identification of DPA ..........................................50
4.6.4 NMR of Lanthanide(III) Complexes ...........................................51
4.7 Crystallography.....................................................................................52
5. DISCUSSION.. ...............................................................................................74
5.1 Acid Dissociation Constants .................................................................74
5.2 Lanthanide(III) Stability Constants.......................................................75
5.2.1 PDA..............................................................................................75
5.2.2 DPA..............................................................................................75
5.2.3 CA ................................................................................................76
5.3 Calorimetry ...........................................................................................77
5.3.1 Ligand Protonation.......................................................................77
5.3.1.1 DPA..................................................................................77
5.3.1.2 CA ....................................................................................77
5.3.2 Change in Enthalpy......................................................................78
5.3.2.1 PDA..................................................................................78
vii
5.3.2.2 DPA..................................................................................78
5.3.2.3 CA ....................................................................................79
5.3.3 Change in Entropy .......................................................................81
5.3.3.1 PDA..................................................................................81
5.3.3.2 DPA..................................................................................81
5.3.3.2 CA ....................................................................................82
5.4.1 PDA..............................................................................................82
5.4.2 DPA..............................................................................................83
5.4.3 CA ................................................................................................83
5.5 Eu(III) Laser Fluorescence ...................................................................84
5.5.1 PDA..............................................................................................85
5.5.2 DPA..............................................................................................85
5.5.3 CA ................................................................................................85
5.6 NMR.. ...............................................................................................86
5.6.1 PDA..............................................................................................86
5.6.2 DPA..............................................................................................86
5.6.3 CA ................................................................................................87
5.7 Crystallography.....................................................................................87
5.8 Conclusions...........................................................................................88
5.8.1 PDA..............................................................................................88
5.8.2 DPA..............................................................................................88
5.8.3 CA. ...............................................................................................89
5.8.4 Steric Hindrance of Aminopolycarboxylate Ligands ..................90
5.8.4.1 Piperidine Ring .........................................................................90
5.8.4.2 CA. ............................................................................................90
5.9 Future Work ..........................................................................................91
APPENDICES
A Hypersensitive Spectroscopy ................................................................104
B Eu(III) Laser Induced Fluorescence......................................................127
C 1H NMR Spectroscopy..........................................................................135
D Crystal Structures..................................................................................141
E Previously Published Data From This Work. ......................................154
REFERENCES
................................................................................................170
BIOGRAPHICAL SKETCH ..............................................................................176
viii
LIST OF TABLES
Table 4.1: The concentration acid dissociation constants for PDA, T =

25.0C, NaClO4 media......................................................................54
Table 4.2: The concentration acid dissociation constants for DPA, T =
25.0C, NaClO4 media ......................................................................55
Table 4.3: The concentration acid dissociation constants* for CA, T = 25.0C,
NaClO4 media ...................................................................................56
Table 4.4: Stability constants of select lanthanide(III) ions with DPA, T =
25.0 C NaClO4 media.......................................................................57
Table 4.5: Stability constants* of select lanthanide(III) ions with CA, T =
25.0 C, NaClO4 media.....................................................................58
Table 4.6: Thermodynamic values for the DPA complexation with Ho(III) or
Nd(III), pH = 5.30 to 5.50, [MES] = 0.100 M, T = 25.000C, I =
0.50 M NaClO4. ................................................................................59
Table 4.7: Thermodynamic values for the CA complexation with Ho(III) or
Nd(III), pH = 5.30 to 5.50, [MES] = 0.100 M, T = 25.000C, I =
0.50 M NaClO4 .................................................................................60
Table 4.8: Values from the linear regressions of Figure 4.1 for the change of
the oscillator strength of Nd(III) when complexed with DPA and
CA, I = 2.00 M NaClO4, pH = 4.50 - 6.00, T = 23C.......................62
Table 4.9: Values from the linear regressions of Figure 4.2 for the change of
the oscillator strength of Ho(III) when complexed with DPA and
CA, I = 2.00 M NaClO4, pH = 4.50 - 6.00, T = 23C.......................64
Table 4.10: The oscillator strengths of Nd(III) and Ho(III) and their
complexes with DPA and CA, I = 2.00 M NaClO4, T= 23C ..........65
Table 4.11: Summary of the peaks observed by fluorescence peaks of Eu(III)
for the various PDA, DPA and CA, I = 0.50 and 2.00 M NaClO4,
T = 23C............................................................................................66
Table 4.12: The nuclear Overhauser effect of PDA at different pH, I = 0.50 M
NaClO4 and T = 25.0C ....................................................................69
Table 4.13: The observed nuclear Overhauser effect of DPA* at different pH,
I = 0.50 NaClO4 and T = 25.0C......................................................71
Table 5.1: Acid dissociation constant values for PDA, DPA and CA................92
ix
Table 5.2: Acid dissociation constant values for IDA, NTA, dipicolinic acid
and hydroxybenzene ..........................................................................93
Table 5.3: The lanthanide(III) stability constants of PDA and DPA, T =
25 C, I = 0.1 M KNO3 .....................................................................94
Table 5.4: Lanthanide(III) stability constants of IDA, NTA and dipicolinic
acid, T = 25 C, I = 0.1 M KNO3 .......................................................95
Table 5.5: Previously determined thermodynamic values of CA with the
lanthanum(III) ion , T = 25C, I = 0.5 M NaClO4 ............................96
Table 5.6: Thermodynamic values for the first protonation of IDA, NTA,
dipicolinic acid, 4-hydroxypyridine and hydroxybenzene, T =
25 C, I = 0.5 M NaClO4 ..................................................................97
Table 5.7: Thermodynamic values of lanthanide(III) complexation with
IDA, NTA, and dipicolinic acid, T = 25 C, I = 0.5 M NaClO4 ......98
Table 5.8: Nd(III) and Ho(III) oscillator strength values for NTA, IDA,
dipicolinic acid and CA ....................................................................101
Table 5.9: Eu(III) fluorescence peaks for acetic acid, dipicolinic acid, CA,
NTA and IDA ligand species............................................................102
Table 5.10: Eu(III) waters of hydration and ligand coordination numbers
for acetic acid, dipicolinic acid, CA, NTA and IDA ligand
species ...............................................................................................103
LIST OF FIGURES
Figure 1.1: Structures of NTA, EDTA and DTPA .............................................9

Figure 1.2: Structures of -picolinic acid and dipicolinic acid ...........................10
Figure 1.3: Structures of PDA and DPA .............................................................11
Figure 1.4: Structural geometries and ring flip of the PDA and DPA.................12
Figure 1.5: Tautomer structures of chelidamic acid ...........................................13
Figure 4.1: The oscillator strength of Nd(III) complexes plotted versus the
ligand to metal concentration ratio, I = 2.00 M NaClO4, pH = 4.50
- 6.00, T = 23C ................................................................................61
Figure 4.2: The oscillator strength of Ho(III) complexes plotted versus the
ligand to metal concentration ratio, I = 2.00 M NaClO4, pH = 4.50
- 6.00, T = 23C ...............................................................................63
Figure 4.3: The chemical shift of the peaks in the 1H NMR spectrum of PDA
versus log of concentration of the deuterium ion, I = 0.50 M
NaClO4 and T = 25.0C. The peak legend refers to proton
assignments given in Figure 4.5 .......................................................67
Figure 4.4: The chemical shift of various peaks in the 1H NMR spectrum of
DPA versus log of concentration of the deuterium ion, I = 0.50
M NaClO4 and T = 25.0C. The peak legend refers to proton
assignments given in Figure 4.6 ........................................................68
Figure 4.5: PDA proton atom designations used with 1H NMR .........................70
Figure 4.6: DPA proton atom designations used with 1H NMR .........................72
Figure 4.7: CA carbon atom designation used with 13C NMR ...........................73
Figure 5.1: The relationship between the residual enthalpy, H, of the first
complex formation with Nd(III) and the total basicity of the
nitrogen donor atoms of select polycarboxylate ligands ..................99
Figure 5.2: Correlation of S1 of Nd(III) and the number of carboxylate
groups with acetate (ac) and select polycarboxylate ligands ...........100
xi
LIST OF ABBREVIATIONS AND SYMBOLS
CA
chelidamic acid
CNL
calculated coordination number of the ligand
DPA
1,2-dicarboxypiperidine-N-acetic acid
DTPA
diethylenetriaminepentaacetic acid
EDTA
ethylenediaminetetraacetic acid
nH2O
number of water molecules in the inner hydration sphere of the Eu(III) ion
nOe
nuclear Overhauser effect
PDA
piperidine-1,2-dicarboxylic acid
PM
oscillator strength of the metal aquo ion
PML
oscillator strength of the ML complex
PML2
oscillator strength of the ML2 complex
xii
ABSTRACT
Piperidine-2,6-dicarboxylic acid (PDA), 2,6-dicarboxypiperidine-N-acetic acid
(DPA) and chelidamic acid (CA) were characterized using a variety of techniques. The
acid dissociation constants of these ligands were determined by potentiometric titration
and 1H NMR. The crystal structures of PDA and DPA were determined using an X-ray
diffractometer.
The stability constants of select trivalent lanthanide ions (La, Nd, Eu, Ho and Lu)
with DPA and CA were determined by potentiometric titration. The oscillator strength of
the Nd and Ho complexes of DPA and CA were determined by spectroscopic titration.
These oscillator strength values were used to examine coordination effects of DPA and
CA on Nd(III) and Ho(III). The 7F0 5D0 selective excitation was used to examine the
inner coordination sphere of the Eu(III) ions upon coordination with DPA and CA. The
number of Eu(III) hydrating water molecules and the calculated ligand coordination
number were determined for all complex species. The H and S of protonation values
and H and S values of Ho(III) and Nd(III) complexation were determined by
calorimetric titration.
The stability constants of PDA could not be determined by potentiometric
titration. Oscillator strength measurements, calorimetric titration and laser fluorescence
indicated only minimal bonding was occurring between the lanthanide(III) ions and PDA.
xiii
CHAPTER 1
INTRODUCTION
1.1 Statement of Problem

Ions of the lanthanide(IIII) series tend to form similar coordination bonds to a
ligand due to the similar charge and size of the cations. Molecules with a flexible
structure can reorient the coordination site around the changing size of the lanthanide(III)
ions and so have similar stability constants for these trivalent metal ions. A more rigid
coordination structure could decrease the stability constant of the ligand but increase the
lanthanide(III) size selectivity of the ligand due to varied coordination distances and the
different radii of the ions. Such compounds could provide improved materials for the
separation of lanthanide(III) or actinide(III) ions.
Aminocarboxylate ligands have been studied for the separation of lanthanide(III),
and actinide(III) ions1,2.
Typically these compounds are straight chain aliphatic
molecules with acetic acid functional groups such as nitrilotriacetic acid (NTA),
ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA).
Many aminopolycarboxylate ligands have a discontinuous trend in their lanthanide(III)
series stability constants which would cause simultaneous elution of several
lanthanide(III) ions from a cation exchange column2. Studies of lanthanide(III) and
actinide(III) complexation with different variations of the structure of the coordination
site of the ligand can add insight into the nature of the aminopolycarboxylate
coordination and may lead to more size selectivity in +3 f-element separations.
1.2 Aminocarboxylate Properties
Compounds that contain at least two carboxylic acid groups bonded to an amine
first appeared in Swiss patents between 1937 to 1940. Studies of alkaline earth and
lanthanide coordination indicated strong metal bonding occurred between the cation and
both the carboxylic acid groups and the amine3,4,5,6,7. These studies led to the use of IDA
and NTA as elution reagents with cation exchange columns for the separation of
lanthanide(III) ions8.
Aminopolycarboxylate ligands were found to have better
lanthanide separation compared to the previously used eluting agent, citrate9,10,11. The
lanthanide coordination complexes of many of these compounds have been studied
including NTA12,13,14, EDTA14,15,16,17 and DTPA14,18,19,20, shown in Figure 1.1. These
molecules consist of an amine bonded to between one and three acetate groups with
multiple units connected by an aliphatic carbon chain. Metal cations can coordinate with
both the oxygen donor of a carboxylic acid and the nitrogen donor of an amine, giving
aminocarboxylate ligands affinity for both hard and soft Pearson acids. Studies have
examined the effects on lanthanide coordination caused by replacing the acetate group
with a longer chain carboxylic acid. Studies have shown that bidentate lanthanide(III)
coordination is most stable upon the formation of a 5-membered ring21,22,23. A metal
coordinated by both the amine and the carboxylic acid forms a 5-membered ring in which
the carboxylate is in an acetate group.
Other studies compared lanthanide(III)
coordination stability of EDTA analogs where the ethylene was replaced with longer
aliphatic chains24,25.
Ethylene groups promote the formation of a 5 member ring
involving the coordination of both amine groups to the metal ion. Both substitution at the
alkyl linking group and the carboxylic acid group demonstrate the importance of forming
5-membered ring structures in bidentate coordination.
Additionally, the effects of
replacing one or more of the acetate groups with a non-coordinating functional group
such as methylene14 or hydrogen14 or coordinating functional groups such as alcohol14 or
phosphonate26 have been studied.
Several studies have characterized the lanthanide(III) coordination chemistry of

the aromatic aminocarboxylates -picolinic acid14,27,28,29 and dipicolinic acid30,31, shown
in Figure 1.2. All of the coordinating functional groups of these molecules have a fixed
geometry due to the rigid, aromatic ring structure. Complexation of the aromatic ligands
can not be compared directly to that of aliphatic ligands because the aromatic amine has
increased electron density and forms shorter, stronger coordination bonds to lanthanide
ions than aliphatic amines14. The rigid structure of dipicolinic acid does not increase the
size selectivity across the lanthanide series compared to IDA, a straight chain aliphatic
molecule with a similar coordination site. Although dipicolinic acid has a discontinuous
stability constant trend across the lanthanide series, this ligand has been used for the
separations of actinide ions from actinide, lanthanide and other metals ions32,33.
1.3 Lanthanide(III) Elements
1.3.1 General Properties
Elements with an atomic number between 57 (lanthanum) and 71 (lutetium) are
included in the lanthanide series. These elements have the gaseous electron configuration
of [Xe]4fn5d06s2 except La ([Xe]4f05d16s2), Ce ([Xe]4f15d16s2), Gd ([Xe]4f75d16s2 ) and
Lu [Xe]4f145d16s2 with the electron configuration of Gd reflecting the stability of the half
filled shell34,35. The lanthanide ions are primarily in the +3 oxidation state because
electrons in outer orbitals significantly shield the f electrons. Other stable oxidations
states observed with lanthanide ions include +2 (Eu and Yb) and +4 (Ce and Tb),
corresponding to vacant, half filled or filled 4f sublevels. The sizes of the +3 lanthanide
ions are similar due to the lanthanide contraction and range from 1.216 for La(III) to
1.032 for Lu(III)36. Due to the decreasing size of the lanthanide ions across the series,
the charge density (Z/rLn) of the ion increases across the series. The primary hydration
sphere number changes from 9 (La(III) to Nd(III)) to 8 (Tb(III) to Lu(III)) due to the
decreasing ionic radius and the increasing charge density with elements between Nd(III)
and Tb(III) having either 8 or 9 waters of hydration37. Because of the similar charge and
size, most lanthanide(III) ions behave similarly both physically and chemically.
Lanthanide(III) ions are more similar to alkali and alkaline earth metals,
coordinating as Pearson hard acids, than to d-block metals, preferring to bind to hard
3
acids like oxygen and fluorine donors than to soft donors like nitrogen and sulfur. The
+3 lanthanides begin to hydrolyze above pH 6 and the hydroxide can readily compete for
coordination of the metal ion at higher pH38. Lanthanide(III) ions can form both inner
and outer sphere complexes.
An inner sphere complex forms through an Eigen
mechanism as the outer sphere complex replaces one or more primary hydration sphere
water molecules39,40,41. The coordination is primarily ionic with a solution coordination
typically ranging from 8 to 9, depending on properties of the ligand, solvent and
concentration42.
1.3.2 Comparison of Lanthanide Ions (4f) with Actinide Ions (5f)
The trivalent charge that is commonly observed for most lanthanide ions is not the
most stable oxidation state for early (Th Pu) actinides or the late actinide nobelium.
The lanthanide(III) ions are similar in size and are commonly used as analogs for
actinide(III) ions42,43. The 5f orbitals are significantly shielded from binding interactions
similarly to the 4f orbitals. The actinide 5f orbitals have greater spatial distribution
compared to the 7s and 7p orbitals than the spatial distribution of the lanthanide 4f
orbitals compared to the 6s and 6p orbitals. The larger spatial distribution increases the
possibility that actinide bonding has a small degree of covalent nature compared to
lanthanide bonding44.
The increased covalency results in actinide elements having
slightly higher affinity for soft electron donors, such as amines. The increased affinity
for soft donors has been used to separate lanthanide and actinide elements by use of a soft
donor system like thiocyanate45 or a ligand with both hard and soft donor groups such as
aminocarboxylates42.
1.3.3 Separation of Lanthanide(III) and Actinide(III) Ions
The actinide(III) and lanthanide(III) ions are separated by the increased affinity of
actinide ions for soft Pearson donors like amines. The slightly increased stability of the
Am(III) complexes has been postulated to be caused by the increased covalency of 5f
versus 4f elements. Calorimetry data has indicated that there is no significant enthalpy
difference between amine coordination bonding of Am(III) and Nd(III) in
aminopolycarboxylate compounds14.
Mssbauer spectroscopy measurements have
shown increased shift values as the actinide oxidation state is increased46.

4
These
increased shift values are taken to be qualitative evidence for an increased An-L covalent
bonding compared to that of Ln-L, and has been attributed to mixing of 5d, 6d and 7s
orbitals47,48.
Solvent extraction and synergistic solvent extraction studies have also
shown enhanced covalent nature in the actinide(III) ions49,50. A mixed donor ligand with
improved size selectivity for lanthanide(III) ions can be used to separate actinide(III) ions
and to separate actinide(III) ions from lanthanide(IIII) ions. The Am(III) and Nd(III) ions
have similar charge and effective ionic radii, 1.106 and 1.109 for 8 coordinate ions,
respectively36. A plot of log AmL versus log NdL for a series of aminopolycarboxylate
ligands has been shown to be linearly related with a slope of 1.142. Actinide(III) ion
elution can be predicted by the elution of similarly sized lanthanide(III) ions. The 4f and
5f ions can then be separated by the increased interaction of an actinide ion with soft
donor groups.
1.3.4 Spectroscopy of Lanthanides
Absorption bands of lanthanide ions arise from both ground state and excited state
electronic transitions with different J-states of the same 4fn configuration, resulting from
different electron distributions in the 4f orbital. The f-f transitions do not change parity
and so are LaPorte forbidden. The f orbitals are well shielded and so the symmetry of the
orbitals is generally not affected by ligand field as commonly occurs in d-d transitions.
Since the ligand field does not relax the selection rules, lanthanide f-f transitions are
weak with molar absorptivities less than 10 M-1 cm-1 and the bands are very narrow.
Some f-f transitions are affected by the ligand field, exhibiting both spectral intensity and
peak positions changes.
These transitions are termed hypsersensitive and have the
following characteristic change in term symbols: S = 0 or 2, |L| 2 and |J| 251.

They follow selection rules for electric quadrupole transitions but have intensities of
electric dipole transitions and have been explained in terms of an inhomogeneous
dielectric surrounding the lanthanide ion derived from the ligand field effect34.
Hypersensitive transitions have also been explained by a charge transfer due to the
covalency of the lanthanide-ligand bond52. Hypersensitive transitions have been used to
distinguish inner sphere and outer sphere complexation53,54,55 and to determine the
coordination number of lanthanide(III) ions in solution56,57.
5
Lanthanide ions also have characteristic luminescence spectra in the visible and
near-IR wavelength regions58,59,60.
Luminescence radiation emissions occur because
lanthanide-ligand radiationless de-excitation processes are relatively ineffective. The

luminescence of Eu(III) and Tb(III) have been studied extensively59. The emission bands
of Eu(III) occur from the 5D0 lowest excited state to the 7FJ ground state where J = 0 to 6.
Since both the excited and ground states of the 7F0 5D0 selective excitation (excitation
from 578 to 581 nm and emission at 614 nm) are nondegenerate and can not be further
split by the ligand field, the wavelength of the excitation occurs at different wavelength
for each different Eu(III) environment. The change of fluorescence intensity and peak
position are related to the number of Eu(III) coordination environments of the system61.
The O-H oscillator is an effective quenching agent of Eu(III) luminescence. This
phenomenon has been explained by an overlap of the = 3 O-H energy level with the 5D0
lowest excited state59.
The O-D oscillator does not quench the luminescence as
effectively and so species have prolonged lifetimes and increased intensity in D2O. The
number of water molecules in the inner hydration sphere of the Eu(III) ion has been
shown to be related to the difference of the fluorescence lifetimes of a species in water
and D2O62.
1.4 Objectives of Present Work
The goal of the present work is to study the interactions of a series of
lanthanide(III) cations (La, Nd, Eu, Ho and Lu) with aliphatic aminocarboxylate ligands
that have structural features that reduce the reorganization of the coordination site such as
piperidine-1,2-dicarboxylic acid (PDA) and 1,2-dicarboxypiperidine-N-acetic acid
(DPA), shown in Figure 1.3. These molecules have a coordination site that is sterically
hindered by the piperidine ring structure which is directly bonded to the carboxylic acid
functional groups.
Most aliphatic aminocarboxylate ligands previously studied are
straight chain molecules in which the carboxylic acid groups are bonded to the amine and
have no other restrictions on the coordination geometry, as discussed in section 1.2. The
acid dissociation constants and lanthanide(III) complex stability constants of PDA63,64
and DPA65 have been previously reported.
The size selectivity of PDA across the
lanthanide(III) series is lower than the straight chain coordination analog iminodiacetic
6
acid (IDA) while DPA was reported to have improved size selectivity across the
lanthanide(III) series compared to the aliphatic structural analog NTA. The ligands and
their lanthanide(III) complexes were not characterized structurally nor spectroscopically.
The coordination geometry of PDA and DPA should be more organized and more rigid
than straight chain aliphatic molecules due to the piperidine ring structure. The increased
rigidity and pre-organization of the coordination site should increase the size selectivity
of the ligands. The piperidine ring exists in either a boat or chair form similar to
cyclohexane. The boat form can convert to the opposite boat form where the axial and
equatorial positions are reversed, proceeding through twist-boat and boat geometries.
This conversion, shown in Figure 1.4, is called ring flip. The interchange of chair and
boat forms of the piperidine ring, ring flip, can cause nitrogen inversion that would
reorient the coordination bonds of the complex, which should decrease the stability of the
complex and decrease the size affinity of PDA and DPA.
The coordination chemistry of chelidamic acid (CA) has been characterized with
some divalent alkaline earth and d-block ions66,67,68 and trivalent lanthanum69. CA is a
coordination analog of dipicolinic acid, but the ring structure has increased flexibility due
to the tautomers, shown in Figure 1.5, that exist simultaneously in solution. The keto
tautomer has been shown to distort the planar structure that is observed in dipicolinic
acid70. The distortion is caused by increased sp3 orbital character of the nitrogen that
causes the amine and the carboxylic acid groups to adapt non-planar orientations. The
bond lengths of the CA piperidine ring vary according to the structure of the keto
tautomer with alkene bonds being shorter and aliphatic bonds being longer than observed
for dipicolinic acid. The increased flexibility of the CA coordination site should decrease
the lanthanide(III) size affinity while the decreased aromatic nature of the CA amine
should decrease the lanthanide(III) complex stability compared to dipicolinic acid.
Straight chain IDA and NTA have similar coordination sites as the piperidine
based PDA and DPA, respectively, but the ring structure should make the coordination
sites more rigid and increase the lanthanide(III) size selectivity of the ligands.
Dipicolinic acid has a similar coordination site as CA but the increased aliphatic nature of
CA should decrease the stability and size selectivity of lanthanide(III) complexes. The
7
stability constants determined by this study should indicate changes in ligand size affinity
by comparison with the stability constants of IDA, NTA and dipicolinic acid across the
lanthanide(III) series. Comparison of the thermodynamic (entropy and enthalpy) values
of complexation determined by this work with the values for aminopolycarboxylate
ligands can provide evidence for changes in the type or length of coordination bonds or
net changes of the systems caused by complex formation. The coordination compounds
of PDA, DPA and CA were examined by Ho(III) and Nd(III) hypersensitive spectroscopy
and Eu(III) laser fluorescence.
The coordination nature of ligands with similar
coordination sites can be compared to show any difference caused by the rigid
coordination geometry or other effects caused by the ring structures. These structural and
thermodynamic differences caused by the additional ligand ring structures can be used to
predict the properties of new ligand structures and suggest new compounds that might
have improved lanthanide(III) ion size selectivity or enable improved lanthanide(III) and
actinide(III) ion separation than current compounds.
HO
HO
OH
HO
O
NTA
HO
OH
OH
N
O
HO
EDTA
O
O
N
HO
O
OH
OH
OH
DTPA
Figure 1.1.
Structures of NTA, EDTA and DTPA .

* NTA = nitrilotriacetic acid; EDTA = ethylenediaminetetraacetic acid; DTPA =
diethylenetriaminepentaacetic acid
OH
HO
O
picolinic acid
N
O
O
dipicolinic acid
Figure 1.2.
Structures of -picolinic acid and dipicolinic acid.
10
OH
HO
HO
OH
N
O
O
O
DPA
PDA
Figure 1.3.
Structures of PDA and DPA.
11
OH
OH
A
H
A
H
A
H
PDA
A
H
A
H
N
A
A
H
A
H
DPA
H
H
Figure 1.4.
Structural geometries and ring flip of the PDA, top, and DPA, bottom. Protons from
meta and para carbon have been omitted for clarity and carboxy groups have been shown
as A.
12
HO
OH
OH
N
O
HO
Figure 1.5.
Tautomer structures of chelidamic acid.
13
OH
N
O
CHAPTER 2
EXPERIMENTAL
2.1 Chemical Reagents

Water that had been purified by a reverse osmosis system and then de-ionized (Epure, Barnstead) was used for preparing aqueous solutions in all experimental
procedures. Concentrated perchloric acid (60%, Fisher Scientific) and sodium hydroxide
(Fisher Scientific) were reagent grade. Standard hydrochloric acid (certified, Fisher
Scientific) and sodium hydroxide (certified, Fisher Scientific) solutions were used
without dilution. The solutions for the calibration of the pH meters were pH 4.00 (
0.01), 7.00 ( 0.01) and 10.00 ( 0.01) standard buffers (Fisher Scientific).
2.1.1 Lanthanide(III) Perchlorate Stock Solutions
Solutions of lanthanide perchlorates were prepared by dissolution of the oxides of
lanthanum (99.999%), neodymium (99.99%), europium (99.999%), holmium (99.999%)
or lutetium (99.99%) (Aldrich Chemical) in concentrated perchloric acid. The solutions
were fumed to near dryness three or more times to remove excess perchloric acid before
dilution with de-ionized water. The metal concentrations were standardized by titration
with an ethylenediaminetetraacetic acid (EDTA) standard solution (0.0946 M, Aldrich
Chemical) using xylenol orange (Aldrich Chemical) as an indicator in acetate buffered
solutions of pH 4.5 that contained a few drops of pyridine71. The solutions were warmed
on a hot plate to 50 to 60C prior to titration to reduce error caused by the slow kinetics
14
involved in the competition between the EDTA and the xylenol orange complexes.
Typical solutions of lanthanide perchlorates were 100.0, 250.0 or 500.0 mL with known
concentrations that ranged from 0.101 to 1.01 M.
The lanthanide perchlorate stock solutions contained an unknown amount of
excess perchloric acid from the dissolution procedure. The perchloric acid concentration
were determined by titration with a standardized sodium hydroxide solution using a
calibrated pH electrode to monitor the acidity change. An endpoint, pH 6.0, was used for
the perchloric acid titration to avoid lanthanide hydrolysis that typically begins around
pH 6.0 to 6.5. The perchloric acid concentrations in the lanthanide perchlorate stock
solutions were calculated as the average value of five or more titrations and were reported
with three significant figures.
2.1.2 Sodium Perchlorate Stock Solutions
Stock solutions of sodium perchlorate (reagent grade, Aldrich Chemical or Acros
Organics) were prepared in volumetric flasks. Samples of sodium perchlorate, weighed
on an analytical balance, were dissolved in de-ionized water. The solutions were filtered
through a 0.45 m nylon filter membrane (Whatman) before use. Typical stock solutions
were 500.0 mL or 1.000 L of known concentrations of sodium perchlorate that ranged
from 6.00 to 8.50 M.
2.1.3 Ligands
The purity of the ligands was checked by determination of the concentration of a
solution by potentiometric titration with a standard base solution.
The calculated
concentrations indicated that the purity of each ligand was 99%.

2.1.3.1 Chelidamic Acid
Chelidamic acid, CA, (97%, Aldrich Chemical) was used without further
purification.
2.1.3.2 Piperidine-2,6-dicarboxylic Acid
Piperidine-2,6-dicarboxylic acid, PDA, was synthesized by Dr. Paul Rickert at
Argonne National Laboratory using the procedure of Anderson and Saito72 that consists
the hydrogenation of pyridine-2, 6-dicarboxylic acid using a platinum oxide catalyst. The
material was used without further purification.
15
2.1.3.3 2,6-Dicarboxypipepridine-N-acetic Acid

2,6-Dicarboxypiperidine-N-acetic acid, DPA, was synthesized by Dr. Paul Rickert
at Argonne National Laboratory using the procedure of Kundra and Thompson73 that
consists of the reaction of chloroacetic acid with PDA. The material was used without
further purification.
2.1.4 Potentiometric Titration Solutions
2.1.4.1 Sodium Hydroxide Standard Solutions
A 4.95 M sodium hydroxide stock solution was prepared by dissolving 396.11g of
sodium hydroxide in a 2.000 L volumetric flask with de-ionized water. All other sodium
hydroxide solutions were made by dilution of this 4.95 M stock solution. To prepare the
sodium hydroxide solutions, sodium perchlorate stock solution was added so that the sum
of the concentrations of sodium perchlorate and sodium hydroxide would give the desired
ionic strength. The sodium hydroxide solutions were standardized by titration with
potassium hydrogen phthalate (A.C.S. acidimetric standard, Aldrich Chemical) that had
been dried at 70.0C in an oven for over a week. Phenolphthalein (A.C.S. reagent,
Aldrich Chemical) was used as the indicator. Stock solutions were typically 500.0 mL or
1.000 L with a known concentration ranging from 0.020 to 0.100 M sodium hydroxide
with an ionic strength of 0.10, 0.50 or 2.00 M.
All standardized sodium hydroxide solutions were stored under nitrogen gas
(DOC grade, Airgas). Prior to use, the nitrogen was bubbled through solutions of 4.00 M
sodium hydroxide solution and sodium perchlorate solution at the ionic strength of the
standardized solution. The sodium hydroxide prevented carbonate contamination of the
base solution by removing carbon dioxide from the nitrogen gas. Bubbling through a
sodium perchlorate solution saturated the nitrogen with moisture in an effort to reduce
evaporation caused by the flow of the gas through the titrant and other experimental
solutions.
2.1.4.2 Perchloric Acid Standard Solutions
All perchloric acid stock solutions were made from concentrated perchloric acid
by dilution with de-ionized water in a volumetric flask.
The perchloric acid stock
solutions were standardized by titration with standardized sodium hydroxide solutions

16
using phenolphthalein as the indicator. The stock solutions were typically 250.0 or 500.0
mL of perchloric acid with known concentration ranging from 0.200 to 0.500 M.
2.1.4.3 Ligand Solutions
Stock solutions of CA, PDA or DPA were prepared in volumetric flasks by
dissolution of a sample of known mass. A stock solution was typically 100.0, 250.0 or
500.0 mL with known concentration ranging from 5.00 to 20.00 mM for PDA or 3.00 to
5.00 mM for CA or DPA.
Experimental solutions of each ligand were made by dilution from the
corresponding stock solution. Aliquots of a sodium perchlorate stock solution were
added to obtain the desired total ionic strength. A typical experimental solution was
10.00 or 20.00 mL with a ligand concentration that ranged from 2.00 to 10.00 mM PDA
or 2.00 to 5.00 mM CA or DPA with an ionic strength of 0.10, 0.50 or 2.00 M.
2.1.4.4 Lanthanide(III) Complex Solutions
Stock solutions of CA, PDA or DPA were prepared as described in 2.1.4.C.
Stock solutions of the desired lanthanide perchlorates were prepared as described in
section 2.1.1.
Experimental solutions of the desired lanthanide to ligand concentration ratio
were made by dilution of the corresponding ligand and lanthanide perchlorate stock
solutions. Aliquots of a sodium perchlorate stock solution were added to obtain the
desired ionic strength. Typical experimental solutions were 10.00 or 20.00 mL with
known ligand concentrations ranging from 2.00 to 10.00 mM PDA or 2.00 to 5.00 mM
CA or DPA, and Ln(III) ion concentrations ranging from 1.00 to 5.00 mM with an ionic
strength of 0.100, 0.500 or 2.00 M.
2.1.5 Laser Induced Fluorescence Solutions
Stock solutions of CA, PDA or DPA were prepared as stated in section 2.1.4.C
and the europium perchlorate stock solution was prepared as described in 2.1.1.
Experimental solutions of the desired Eu(III):ligand concentration ratio were
made by dilution of these ligand and europium perchlorate stock solutions. Aliquots of a
sodium perchlorate stock solution were added to create the desired ionic strength.
Typical experimental solutions were prepared in 25.00 or 50.00 mL volumetric flasks
17
with concentrations ranging from 1.00 to 2.00 mM Eu(III) ion, 0 to 10.00 mM PDA or 0
to 5.00 mM CA or DPA with an ionic strength of 2.00 M. The pH was adjusted with
2.00 M sodium hydroxide and 2.00 M perchloric acid solutions. Some samples were
prepared with constant Eu(III) ion and ligand concentrations while the pH varied between
2.00 and 6.00. Other samples were prepared with constant Eu(III) ion concentration and
pH between 5.00 and 6.00 with varying ligand concentrations. A reference solution of
0.100 M europium perchlorate solution was prepared at pH 3.50 and 2.00 M ionic
strength.
2.1.6 Hypersensitivity Spectroscopy Solutions
Stock solutions of CA, PDA or DPA were prepared as stated in section 2.1.4.C
and the holmium and neodymium perchlorate stock solutions were prepared as stated in
section 2.1.1.
Experimental solutions of the desired lanthanide to ligand concentration ratios
were made by dilution of these ligand and lanthanide perchlorate stock solutions to which
aliquots of a sodium perchlorate stock solution were added to obtain the desired ionic
strengths. Typical experimental solutions were prepared in 25.00 mL volumetric flasks
with concentrations ranging from 0 to 5.00 mM Ho(III) ion, 0 to 5.00 mM Nd(III) ion, 0
to 10.00 mM PDA and 0 to 5.00 mM CA or DPA with an ionic strength of 2.00 M. The
pH was adjusted using 2.00 M sodium hydroxide and 2.00 M perchloric acid solutions.
Some samples were prepared with constant Ln(III) ion and ligand concentrations while
the pH was varied between 2.00 and 6.00. Other samples were prepared with constant
Ln(III) ion concentration and a pH between 5.00 and 6.00 while the ligand concentrations
were varied.
2.1.7 Nuclear Magnetic Resonance Solutions
2.1.7.1 Solutions for Adjusting pH
A 0.50 M stock solution of perchloric acid was prepared by dilution of
concentrated perchloric acid with deuterium oxide (Cambridge Isotope Laboratory). The
perchloric acid introduced a proton impurity into the deuterium solvent that would appear
as a peak normally associated with water in 1H NMR spectra. The molecules of this
study had peaks ranging from 1.0 to 4.5 ppm with no significant overlap with the water
18
peak which typically ranged from 5 to 5.5 ppm in 1H NMR spectra. Solutions were
stored in a desiccator when not in use to minimize additional proton contamination from
atmospheric water since an excessively large water proton peak could cause a loss of
sensitivity for other 1H NMR peaks
A 0.50 M sodium deuteroxide solution was prepared by dilution of a 40% sodium
deuteroxide solution (Aldrich Chemical) with deuterium oxide. Solutions were stored in
a desiccator when not in use to reduce contamination from atmospheric carbon dioxide
and water vapor.
2.1.7.2 Ligands Solutions
Solutions of CA, PDA or DPA were prepared in 10.00 mL volumetric flasks by
dissolution of a sample of known mass in deuterium oxide. The sodium salt of 3(trimethylsilyl)-1-propanesolfonic acid, DSS, (98%, Aldrich Chemical) was added to
each 1H NMR sample as a 1H peak position reference. The typical concentrations of the
ligands ranged from 4.00 to 5.00 mM for DPA, 10.00 to 15.00 mM for PDA or 5.000
mM for CA. Two samples of each ligand were prepared for pH titration experiments.
Perchloric acid was added to the first sample to create the 0.50 M ionic strength and the
solution was titrated with 0.50 M sodium deuteroxide. Sodium deuteroxide was added to
the second sample to create the desired 0.50 M ionic strength and the solution was titrated
with 0.50 M perchloric acid. This approach was used to minimize any NMR sensitivity
problems due to the dilution that occurs during the course of the titration.
2.1.7.3 Lanthanide(III) Complex Solutions
Lanthanum, lutetium and europium perchlorate stock solutions were prepared as
described in section 2.1.1. Solutions of CA, PDA or DPA were prepared in 100.0 mL
volumetric flasks by dissolution of a sample of known mass in deuterium oxide. Aliquots
of the lanthanum or lutetium perchlorate stock solutions were added to obtain the desired
Ln(III) ion concentration. The sodium salt of DSS was added to each 1H NMR sample to
provide a 1H peak position reference. Typical concentrations of the ligands ranged from
4.00 to 5.00 mM for DPA, 10.00 to 15.00 mM for PDA or 5.00 mM for CA. Two
different concentrations of the Ln(III) ions were used for each ligand so that the mole
ratio of metal to ligand ratio was 1:1 or 1:2 for the particular ligand solution. Aliquots of
19
perchloric acid were added so that the total ionic strength of the solution was 0.50 M.
The solution was titrated with 0.50 M sodium deuteroxide.
2.1.8 Crystals
DPN and PDA were dissolved into de-ionized water. The solutions were covered
and were stored at room temperature to allow slow evaporation of the solvent. After
several weeks, crystals were collected from each solution. The crystals were examined
under a microscope so that single crystals could be extracted and mounted for
diffractometer measurements.
2.1.9 Calorimetry Solutions
2.1.9.1 Standard Solutions
A 0.1000 M hydrochloric acid solution was used as the titrant in all
standardization titrations. A 0.1000 M sodium hydroxide solution was boiled for 30
minutes to remove carbon dioxide contamination before calorimetric titration. A 0.1 M
solution of tris(hydroxymethyl)aminomethane (reagent grade, ICN), THAM, was
prepared in a 250.0 mL volumetric flask by dissolution of a sample of known mass. An
aliquot of hydrochloric acid was added so that 10% of the THAM was protonated.
Scrubbed nitrogen gas (section 2.1.4.A) was bubbled through the THAM solution for 30
minutes to remove carbon dioxide contamination before titration.
2.1.9.2 Ligand Solutions
Solutions of CA, PDA or DPA were prepared in a 100.0 or 250.0 mL volumetric
flask by dissolution of a sample of known mass. Aliquots of a sodium perchlorate stock
solution were added so that the total ionic strength was 0.50 M. Sodium hydroxide was
added until completely neutralization of the ligand to measure the heat of protonation.
The solutions used in the measurement of the heat of complexation were buffered with 4morpholineethanesulfonic acid, MES, (Aldrich Chemical) which does not form
complexes with Ln(III) ions and does not contribute to the ionic strength of a solution.
Fresh buffer stock solutions were made weekly because MES is biologically active. The
MES concentration of each solution was 0.100 M. A 0.100 M sodium hydroxide solution
was used to adjust the pH to between 5.30 and 5.50. Typical solutions were prepared
20
with known concentrations ranging of 15.00 mM for PDA or 10.00 to 20.00 mM for CA
or DPA.
2.1.9.3 Lanthanide(III) Perchlorate Solutions
Lanthanide(III) perchlorate stock solutions were prepared as described in 2.1.1.
The Ln(III) ion solutions were prepared by dilution from the corresponding stock
solution. Aliquots of sodium perchlorate stock solution were added to obtain a total ionic
strength of 0.50 M. The MES buffer concentration of each sample was 0.100 M and the
pH was adjusted to between 5.30 and 5.50 with 0.10 M sodium hydroxide solution.
Solutions were typically 100.0 mL with a known concentration of the Ln(III) ion ranging
from 1.00 mM to 3.00 mM.
2.2 Equipment
2.2.1 Mass Determination
A Fisher Scientific model XA-100 analytical balance was used for all weight
determinations under 100 g. A Fisher Scientific model XL-3000 analytical balance was
used for all weight determination above 100 g. The mass of samples was determined to
at least 4 significant figures.
2.2.2 Potentiometric Measurements
All pH measurements of bulk solutions were performed using a Fisher Scientific
model 950 pH/ion meter equipped with an external temperature sensing probe. The
electrode was either a Corning micro combination Ag-AgCl reference glass electrode or a
Corning semi-micro combination Ag-AgCl reference glass electrode. The potassium
chloride electrolyte solution in the electrodes was replaced with 1.00 M sodium chloride
for the micro electrode and saturated sodium chloride for the semi-micro electrode. The
potassium chloride electrolyte solution was replaced to prevent potassium perchlorate
precipitation in the junction when the electrode is used in high molarity sodium
perchlorate solutions. All measurements were made at room temperature, 23 1C.
2.2.3 Potentiometric Titrations
The potentiometric titration system was designed and built in the laboratory and is
an updated model of the instrument described by Crooks74 and Redko75. The experiments
were performed under nitrogen gas that had been bubbled through solutions of 4.0 M
21
sodium hydroxide to remove carbon dioxide and sodium perchlorate of the same ionic
strength as the experiments to saturate the gas with water vapor. Each titration was
performed with constant stirring using a Corning model PC 420 stirrer/hot plate and
constant temperature, 25.0 0.1C, regulated by a NESLAB model RTE 100
thermostated bath. A Metrohm Dosimat 665 burette was used to titrate additions to the
experimental solution. An Orion Ross epoxy combination electrode filled with a
solution of saturated sodium chloride was connected to a Keithley model 195A digital
meter to monitor the pH of the experiment solution. The system was interfaced to a
computer that operated software prepared in the laboratory to control burette additions
and to record the mV reading of the electrode.
The software has a measurement cycle that is designed to ensure that the sample
had adequate time to reach equilibrium. The readings, measured after a delay time that
ranged between 30 and 120 s, were accepted if they agreed within the user selected
electrode stability parameter, typically 0.1 mV. After two consecutive readings of the
electrode that agreed within the electrode stability parameter, the data point was
recorded and the system made the next titration addition. If consecutive readings failed
to agree within the electrode stability parameter by the tenth electrode reading, the
tenth electrode reading was recorded and the system made the next titrant addition. After
the addition was made, the system waited a mixing time, typically 30 s, before restarting
the measurement cycle. Several experiments were performed with a significantly longer
delay time. The results from these experiments were compared to experiments with
shorter delay times to ensure that the shorter times were adequate for the system to reach
equilibrium. This approach ensured that data from the shorter delay time experiments
were not due to very slow kinetics or from readings that failed to meet the electrode
stability criteria.
2.2.4 Laser Induced Fluorescence
2.2.4.1 Fluorescence Spectra
Fluorescence experiments were performed on solutions in a 1 cm quartz cell using
a Nd-YAG laser (Quanta Ray DCR 2A, Spectra Physics) coupled to a pumped dye laser
(Quanta Ray PDL2, Spectra Physics). The laser dye was a 1:1 solution of Rhodamine
22
590 tetrafluoroborate (Exciton) and Rhodamine 610 perchlorate (Exciton) in methanol

(HPLC grade, Fisher). The concentration of the amplifier was 0.100 mM for both dyes
while that of the oscillator was 0.016 mM for both dyes. The dye was pumped by the
second harmonic output of the Nd-YAG laser at 532 nm which gave a laser power of
approximately 15 mJ at 580 nm.
The excitation monochromator (Jarell-Ash) was
controlled with a computer interfaced stepper motor that allowed scanning of the dye
laser emission throughout the entire range of the emission wavelength of the dye. The
fluorescence was detected perpendicular to the incident beam using a Hamamatsu R928
photomultiplier tube. The system was operated by software that had been written by Dr.
L. J. van de Burgt of the FSU laser laboratory which controlled the stepping motor of the
laser and recorded the peak position and intensity.
The stability of the laser was
measured at various times during the experiment using a calibrated Scientech model
380101 volume calorimeter attached to a Laser Precision model RT-7620 energy
ratiometer.
2.2.4.2 Fluorescence Lifetime Measurements
Lifetime measurements were performed at a fixed wave number corresponding to
the maxima of the fluorescence peak intensity of each spectrum. Fluorescence decay
curves were collected using a LeCroy 9410 Dual 150 MHz oscilloscope. The data was
transferred to a computer using software supplied with the oscilloscope. The software
had been modified by Dr. van de Burgt.
2.2.5 Hypersensitivity Spectroscopy
Ultraviolet-visible spectrophotometric measurements of Nd(III) and Ho(III) ions
were made in 10 cm glass cells using a dual beam Cary 14 UV-visible spectrophotometer
that has been upgraded by On Line Instrument Systems (OLIS).
The system was
interfaced with a computer to allow automated acquisition and storage of data. The light
source was a tungsten lamp and the signal was collected by a photomultiplier tube.
2.2.6 NMR
All 1H NMR titration experiments were performed with a Varian INOVA 500
MHz NMR spectrometer using a 5 mm quad nucleus detection probe. All 1H decoupled
13
C NMR spectra and homonuclear decoupled 1H NMR spectra were measured using a
23
Bruker AC 300 MHz NMR spectrometer using a 5 mm dedicated 1H/13C probe. The
NMR tubes were not spun during any experiments.
2.2.7 Crystallography
Crystallography was performed on a Bruker SMART APEX diffractometer at
25.0C using a CCD detector.
2.2.8 Calorimetry
The calorimeter, designed and built in the laboratory, is an updated model of the
calorimeters described by Orebaugh76, Ensor77 and Caceci78. The water bath was kept at
25.000C by competition between a cooling coil connected to a Fisher Scientific model
9500 Isotemp refrigerated circulating water bath and a heating element controlled by a
Tronac PTC-49 temperature controller which maintained the bath to 0.001C79. The
calorimetry cup was a gold plated glass beaker inside a copper housing. The instrument
operated in a semi-adiabatic mode using a Melcor model FC0.6-32-06L Peltier
heating/cooling device in contact with the exterior of the gold plated beaker to stabilize
the temperature during the course of a titration. After a measurement was made, the
Peltier heating/cooling device was used to reestablish the original operating temperature
of the cup through minor heating or cooling to remove the thermal effects of the reaction.
Calibration was performed after every fourth or fifth measurement during the titration by
a Tronac model 87-249 heating element that was connected to a Power Designs model
2005 precision power source.
Temperature readings were made with a YSI model
SP033-108 thermistor connected to a Keithley model 181 nanovoltmeter. The Peltier

heating/cooling device, heating element and thermister were housed inside the
calorimetry cup. A motor, mounted to the top of the apparatus was connected to a long,
bladed glass rod, stirred the solution in the calorimetry cup.
The instrument was
interfaced to a computer and managed by software written by Dr. M. Caceci76 that

controlled the Radiometer Copenhagen ABU-80 Autoburette, calibration heating element
and Peltier heating/cooling device and recorded the nanovoltmeter reading. The average
temperatures were measured by the software and typically had a standard deviation less
than 20 x 10-6C after several minutes of data collection. The program ran multiple
24
titrations for each experiment and reported both the individual values and average value
of the heat per addition.
2.3 Procedures
2.3.1 Potentiometric Measurements
Electrodes were calibrated with pH 7.00 and 4.00 buffers for measurements in
acidic media and pH 7.00 and 10.00 buffers for measurements in basic media. The
efficiency of the electrode calibration was maintained above 0.95. Electrodes were
allowed to equilibrate for 1 day prior to use after the sodium chloride solutions were
added as suggested by Corning. Electrode readings were taken after the measurement
had stabilized as shown by the indication on the meter.
2.3.2 Potentiometric Titrations
The sample holder was washed several times with de-ionized water and dried
thoroughly before each experiment. The solutions were placed in the thermal jacketed
sample holder that was connected to a temperature bath and were allowed several
minutes to reach thermal equilibrium. The stirrer was set at the same setting for all
experiments.
A 0.1 mV value was selected as the maximum difference between
consecutive readings for all experiments.

2.3.2.1 Standardization
The electrode was calibrated by the titration of a standardized strong acid with a
standardized strong base to provide a mV to pcH conversion equation. Aliquots of a
standardized perchlorate acid solution and of a sodium perchlorate stock solution were
added to de-ionized water to create 10.00 to 20.00 mL solutions with known
concentrations. These solutions were typically 0.00500 to 0.02000 M perchloric acid
with an ionic strength of 0.100, 0.500 or 2.00 M. This solution was titrated with the
standardized base of the same ionic strength with no less than 10 additions to complete
the titration using typical addition sizes ranging from 0.050 to 0.200 mL.
The
concentrations of the acid and the burette addition size were chosen so that approximately
half the data points in the titration curve were in the acidic and half in the basic regions.
The mixing time after titrant addition was 30 seconds. The delay between the readings
25
was 30 s. Standardization titrations were conducted once for every 1 to 3 experimental

titrations.
2.3.2.2 Acid Dissociation Constant Determination
Aliquots of ligand and sodium perchlorate stock solutions were combined to
create 10.00 to 20.00 mL of a solution with known concentration.
The ligand
concentration of these solutions ranged from 3.00 to 10.00 mM for PDA or 3.00 to 5.00
mM for CA and DPN. The experiments were performed at ionic strengths of 0.100,
0.500 and 2.00 M. The burette addition size, typically 0.030 to 0.100 mL, was chosen so
that 80 additions would cover a pH range from 2.0 to 11.5. The mixing time after titrant
addition was 30 seconds. The delay between the readings was 30 or 120 s.
2.3.2.3 Stability Constant Determination
Aliquots of ligand, lanthanide(III) perchlorate and sodium perchlorate stock
solutions were combined to create 10.00 to 20.00 mL of a solution with known
concentration. The concentrations of these solution ranged from 3.00 to 10.00 mM for
PDA, 3.00 to 5.00 mM for CA or DPA and 2.00 to 5.00 mM for Ln(III) ions. The
experiments were performed at ionic strength of 0.100, 0.500 and 2.00 M. The burette
addition size was chosen such that 80 additions would cover a pH range from 2.0 to 6.0
for most experiments and was typically 0.006 to 0.050 mL. This pH range was selected
to avoid lanthanide hydrolysis and any data points with pH greater than 6.0 were
discarded. When the concentrations of CA and DPA exceeded twice the concentration of
the metal ion, lanthanide hydrolysis did not occur and so a few titrations of CA and DPA
complexes were run with a pH range of 2.0 to 11.5. Other titration parameters were the
same as those used in the determination of acid dissociation constants as described in
2.3.2.B.
2.3.3 Laser Induced Fluorescence
2.3.3.1 Fluorescence Experiments
The 1 cm quartz fluorescence cell was rinsed three times with the sample before
being filled with the sample solution. The room light was reduced during the experiment
to minimize background scattered light. The laser was run for 10 minutes before use in
experimental measurements to allow for operational equilibrium. The laser power was
26
determined by directing the path of laser beam into a volume calorimeter80 and
equilibrium was defined as a constant energy reading over 30 s. The energy was checked
periodically during use and was found to remain constant. Excitation spectra were
collected as the average of 50 pulses per data point over a range of 17210 to 17320 cm-1
in 1 cm-1 increments. A europium standard was run with each experiment to calibrate the
wave number of the laser emission using the position of the peak of the fully hydrated
europium ion.
2.3.3.2 Fluorescence Lifetime Experiments
Samples were measured in a similar fashion to the fluorescence experiments
except that the dye laser was tuned to a fixed wave number corresponding to the maxima
of the peaks from the fluorescence spectra. The fluorescence decay curve was the
average of 1000 fluorescent decay measurements.
2.3.4 Hypersensitivity Spectroscopy
The Cary 14 was turned on at least 30 minutes prior to use to allow operational
equilibration as determined from comparison of the intensity of a standard neodymium
solution over time at selected wavelengths. Experiments were performed in a set of 10
cm glass cells made in the departmental glass shop. The cells were labeled to ensure
similar orientation in all experiments. The reference cell was filled with de-ionized water
and placed in the reference compartment of the Cary 14. The same cell was used as the
reference throughout all experiments. The sample cell was emptied and rinsed three
times with the sample solution before being completely filled with this solution and
placed in the Cary 14 sample compartment. The spectra were measured over the range of
425 to 475 nm for holmium and 555 to 605 nm for neodymium in 1 nm increments. Each
data point is the averaged value of 50 readings. Each experimental set included one
solution of the completely hydrated, uncomplexed Ln(III) ion to ensure standardization of
peak position and oscillator strength between different measurements.
2.3.5 NMR
2.3.5.1 pH Titrations
The sample was placed in a Kontes 5 mm glass NMR tube. The pH was adjusted
by small additions of the acid or base solution and was measured by a calibrated micro
27
electrode inserted directly into the NMR tube. The samples were placed in the Varian
INOVA 500 MHz NMR spectrometer sample compartment that was operated at 25.0
0.1C. The 2H signal was used to optimize the magnet homogeneity and was used as a
lock signal by the spectrometer during 1H measurements. The spectra were measured
using the standard 2 pulse experiment protocol of the Varian software with the first pulse
width set to 0 s and the delay times set to 0 s. The second pulse width was set to the
experimentally determined 90 pulse width, 22.2 s. The acquisition time was 2.048 s.
The data was collected as 16, 32 or 64 transients to produce spectra with a spectral width
of 4000 Hz and a digital resolution of 0.244 Hz. All of the decouplers were turned off.
The chemical shift scale was set at 0 ppm using the reference peak of DSS. The
acquisition time was considered an adequate relaxation time since this experiment was
measuring the change in chemical shift of each peak and not the integration of the
individual peaks.
2.3.5.2 Coalescence Experiments
Each NMR peak of DPA broadened and lost mutliplicity between pH 8 and 9.
The peaks from DSS showed no change in this pH region. The broadening and loss of
multiplicity in the DPA peaks showed the characteristics of a coalescence peak for an
equilibrium involving kinetics that were occurring on a similar time scale as the NMR
measurements.
Experiments were performed similarly to those of the pH titration
experiments in section 2.3.5.A except that the temperature was varied between 25.0 and
5.0C in 5.0C increments in an attempt to resolve the coalesced peaks. The instrument
and sample were allowed 1 hour to equilibrate thermally after each temperature
adjustment as suggested by Dr. T. E. Gedris of the FSU NMR laboratory.
2.3.5.3 Nuclear Overhauser Effect Experiments
The nuclear Overhauser effect (nOe) spectra were collected in the same manner as
in the pH titration experiments in section 2.3.5.A except the standard cyclic nOe
experiment protocol of the Varian software was used.
These experiments were
performed on solutions of PDA and DPA at pH 2.00 and 11.00.
An additional
experiment was run on a solution of DPA at pH 9.00. Each measurement was preceded
by 32 scans to allow the thermal excitation caused by the radio frequency excitation
28
pulses to reach a steady state before the collection of experimental data. The spectra
were collected with an acquisition time of 2.048 s, a spectral width of 4000 Hz and a
digital resolution of 0.244 Hz. Each excitation was performed by 70 pulses of the time
interval, , of 0.10 ms as recommended by Varian. The frequency of the excitation pulses
was set to the selected peak position with the correct multiplicity pattern set by the user.
All decouplers were off.
2.3.5.4 13C 1H Decoupled Spectra
These measurements were performed by Dr. Gedris on the Bruker AC 300 MHz
NMR spectrometer. The 2H signal was used to optimize the magnet homogeneity and as
a lock signal by the spectrometer during measurements. The spectra were collected with
a pulse width of 4.9 s, a spectral range of 17800 Hz and a digital precision of 1.090 Hz.
Several thousand scans were collected to produce a spectrum. The 1H signals were
suppressed in order to decouple the 1H and
13
C signals.
This decoupling removed
multiplicity from the 13C peaks, causing the signals to have greater intensity and allowing
easier comparison of the peak positions. The experiments were performed at room
temperature, 23 1C.
2.3.5.5 1H Homonuclear Decoupled Spectra
The measurements were performed by Dr. Gedris on the Bruker AC 300 MHz
NMR spectrometer at room temperature, 23 1C. The 1H spectra were collected with a
pulse width of 5.0 s, a spectral range of 3200 Hz and a digital precision of 0.391 Hz. A
1
H spectrum was collected while an individual 1H peak was suppressed.
For each
molecule, a series of spectra were collected with the sequential suppression of each
individual 1H peak. In some cases, a 1H spectrum was collected while multiple 1H peaks
were suppressed.
2.3.6 Crystallography
The crystallographic experiments were performed by Dr. Ronald J. Clark of the
FSU Chemistry Department. A crystal of the sample was mounted on a nylon loop and
centered in the diffractometer. The detector distance was 5 cm. The X-ray diffraction
pattern was collected at a specific incident angel over 10 s as a data set called a frame.
Each sample was measured with 1850 frames. Measurements were made at an incident
29
angle up to 28. The integration of the frames was performed using the program SAINT
(Bruker, 1999). No absorption correction was used. The structure was solved by direct
methods and refined by the program SHELXTL (Bruker, 2000). The atoms other than
hydrogen were refined anisotropically and the hydrogen atoms were assigned by least
squares refinement.
2.3.7 Calorimetry
The water bath temperature and heating element were monitored and adjusted for
several weeks using a thermometer to ensure the temperature was stable at 25.000
0.001C. All titrations were performed at this temperature.
The burette was filled with the titrant and the system was flushed thoroughly to
remove all air bubbles. A small air bubble was left in the tip of the burette to prevent
diffusion of the titrant into the sample. The sample was placed in the calorimetry cup
and, after assembly, the calorimetry cup and burette tubing were submerged in the water
bath for at least 10 hours of stirring to allow thermal equilibration. The thermister was
connected to a nanovoltmeter by a Wheatstone bridge. The Wheatstone bridge was used
to adjust the zero point of the thermister to the temperature of the cup. A titration of
water into water was performed with 25 or 50 additions of 0.100 mL to check the zero
point setting of the Wheatstone bridge. After each titration, the Wheatstone bridge was
adjusted to set the zero point to as close to 0 mJ per addition as possible.
A sample of the sodium hydroxide solution was placed in the calorimetry cup
before assembling the apparatus to allow it to come to thermal equilibrium after
placement in the bath. Standardization titrations were performed after both 10 hours and
2 days of thermal equilibration time. These results of the titrations agreed within error,
indicating that 10 hours was adequate time for thermal equilibrium of the calorimetry cup
apparatus to occur.
2.3.5.1 Heat of Dilution
The calorimetry cup was filled with 50.00 mL of a solution with the same ionic
strength, pH and MES concentration as the titrant solution. The system was immersed
and allowed to come to thermal equilibrium for at least 10 hours before a titration. The
solution was titrated by 25 or 50 additions of 0.200 mL of the titrant.
30
2.3.7.2 Standardization
Titrations of 0.1000 0.0005 M standard sodium hydroxide solution by 0.1000
0.0005 M standard hydrochloric acid solution were performed to calibrate the instrument
by measuring the heat of neutralization. The calorimetry cup was filled with 50.00 mL of
the standard sodium hydroxide solution and placed in the water bath for at least 10 hours
with stirring to reach thermal equilibrium. The solution was titrated by 25 or 50 additions
of 0.100 or 0.050 mL of the standard hydrochloric acid solution. The average value
obtained from the standardization titrations was -52.4 2.1 kJ/mole and was within two
standard deviations of the value reported by Grenthe81 of -55.84 0.01 kJ/mole.
An additional standardization was performed using THAM. A 50.00 mL aliquot
of the 0.1 M THAM solution was placed in the calorimetry cup and was titrated by
0.1000 0.0005 M hydrochloric acid. The change in enthalpy was determined to be
-45.6 1.0 kJ/mol for the proton addition and was within two standard deviations of
values found in the literature, -47.53 kJ/mol82, -47.48 kJ/mol83 and 47.36 kJ/mol84.
2.3.5.3 Heat of Protonation
A 50.00 mL aliquot of a solution of the neutralized ligand, as discussed in section
2.1.9.B, was added to the calorimetry cup and allowed to thermally equilibrate for at least
10 hours. The system was titrated with 0.1000 0.0005 M perchloric acid at the same
ionic strength as the ligand solution.
2.3.5.4 Heat of Complexation
The calorimetry cup was filled with 50.00 mL of the Ln(III) ion solution. The
burette was filled with the ligand solution with the same ionic strength, pH and MES
concentration. The calorimetry cup was immersed and allowed to come to thermal
equilibrium for at least 10 hours. The solution was titrated with 25 or 50 additions of
0.100 mL of the ligand solution in studies measuring the formation of the ML species or
both the ML and ML2 species.
31
CHAPTER 3
DATA TREAMENT
3.1 Potentiometric Titrations
3.1.1 Electrode Calibration

The electrode used for acid dissociation constant and stability constant
determinations was calibrated by titration of a standardized perchloric acid solution by a
standardized sodium hydroxide titrant.
The concentration of the hydrogen ion was
calculated for each titrant addition from the concentrations and volumes of the acid and
base solutions, the total volume of the solution and the water ionization constant for the
specific ionic media85.
The electrode readings plotted versus log (hydrogen ion
concentration), pcH, from an acid-base standardization titration was fitted by Excel 98

(Microsoft) using the equation:
y = mx + b
Eq. 3.1
where y was the mV reading of the electrode and x was the calculated pcH value. The
data points between pcH 4.5 and 9.5 were excluded from the linear fit of calibration
titrations as is the standard practice86. Data in this pcH range is excluded because small
errors in the concentrations and volumes of reagents could have large effects on the
electrode reading.
All of the linear fits of acid-base calibration had correlation
coefficients better than 0.9900.
32
The linear fit from calibration titrations was used to calculate the pcH from the
mV readings in titrations of the ligands and the metal ligand complexes. The slope
determined from each acid-base standardization titration at the same ionic strength was
nearly constant, having a standard deviation of less than 0.1 %. Therefore, the average
value of the slope was used in the mV to pcH conversion for a given ionic strength.
Significant fluctuations were seen in the intercept value of the linear fit, ranging from 6.0
to 8.3. The intercept values measured on a particular day at the same ionic strength
tended to agree well so the pcH was calculated using the average of these daily values.
3.1.2 Acid Dissociation Constant Determination
The stepwise acid dissociation equilibrium of DPA can be described by the
equations:
L-m + H+ = HL1-m
Eq. 3.2
HL1-m + H+ = H2L2-m
Eq. 3.3
H2Lm + H+ = H3L3-m
Eq. 3.4
4-m
H3L + H = H4L
Eq. 3.5
where L is ligand and the m = 3 for DPA. The corresponding acid dissociation constants
are defined as:
Ka1 =
[HL]
[H][L]
Eq. 3.6
Ka 2 =
[H 2 L]
[H][HL]
Eq. 3.7
Ka 3 =
[H 3 L]
[H][H 2 L]
Eq. 3.8
Ka 4 =
[H 4 L]
[H][H3 L]
Eq. 3.9
where Ka is the concentration acid dissociation constant, the species concentrations are in
molarity, the species charges have been omitted. CA and PDA have 3 acidic sites so the
stepwise acid dissociation equilibrium can be described by Eq. 3.2, 3.3 and 3.4 with m =
2 and using the corresponding acid dissociation constants, Eq. 3.6, 3.7 and 3.8. These
33
constants were calculated from the potentiometric titration of the ligand with a
standardized base using PSEQUAD.
3.1.3 Lanthanide(III) Complex Stability Constant Determination
The formation of first and second Ln(III) complexes are described by the
equations:
M3+ + Lm-3 = [ML]3+m-3
Eq. 3.10
M3+ + 2 Lm-3 = [ML2]2m-3
Eq. 3.11
where M is the Ln(III) ion, L is the ligand and m = 0 for DPA or m = 1 for PDA and CA.
The corresponding stability constants are defined as:
1 = K 1 =
K2 =
[ML]
[M][L]
[ML2 ]
[ML][L]
2 = K 1K 2 =
[ML 2 ]
[M][L]2
Eq. 3.12
Eq. 3.13
Eq. 3.14
where K1 and K2 are the concentration equilibrium constants for the stepwise formation
of the complexes, 1 and 2 are the stability constant of the ML and ML2 species, the
species concentrations are in units of molarity and the charges of the species have been
omitted. These constants were calculated from the potentiometric data obtained from the
titration of the ligand complex solution with a standardized base using the PSEQUAD
software.
3.2 PSEQUAD
Zkny and Nagypl87 developed the Fortran based computer program

PSEQUAD for the evaluation of potentiometric and/or spectrophotometric equilibrium
data using analytical derivatives. This program is designed to use a Newton-Raphson
procedure to calculate the values of the mass balance and a Gauss-Newton method to
refine equilibrium constants and molar absorptivities. The mass balance is then fitted to
the experimental titration curve using the selected chemical model. The non-interactive
program can fit multiple data sets simultaneously and can give statistical information
such as the partial, total and multiple correlation coefficients for the fitted parameters as
34
well as a statistical error on the determined values. PSEQUAD has a statistical parameter
that can give an indication of how the selected chemical model of the system fitted the
experimental data.
3.3 Laser Induced Fluorescence
3.3.1 Fluorescence Lifetime Measurements
The intensity of the fluorescence emission of the 7F05D0 excitation of Eu(III)

has been shown to be inversely proportional to the number of water molecules in the
inner hydration sphere of the ion59,62. The dipole moment of an oxygen-hydrogen bond
can oscillate with a similar energy as the excited state of the Eu(III) ion and so water and
other molecules that contain an oxygen-hydrogen bond can provide a possible quenching
mechanism of the Eu(III) fluorescence.
It has been shown that the lifetime of the
fluorescence is proportional to the number of water molecules in the inner hydration

sphere of the ion62,88. The lifetime of the fluorescence decay of the various Eu(III)
species was fitted using Sigma Plot 4.0 (Jandel Scientific) with the mono-exponential
decay equation:
y = yoe-kx
Eq. 3.15
where y was the fluorescence intensity, x was time in s, yo was the initial intensity and k
was the fluorescence decay rate constant in s-1. All fluorescence decay curves had a
correlation coefficient fit better than 0.9990. The number of water molecules in the inner
coordination sphere can be calculated using the equation89:
nH2O = 1.07k 0.62
Eq. 3.16
where nH2O is the number of water molecules in the inner hydration sphere of the Eu(III)
ion. The number of inner sphere water molecules was reported with a relatively high
uncertainty, 0.5, due to the potential of a small degree of quenching of the Eu(III)
excited state by oxygen-hydrogen bonds in the outer coordination spheres89. The number
of coordination sites of the ion being occupied by the ligand was calculated as the
difference between 9 and nH2O, assuming the fully hydrated Eu(III) ion has 9 water
molecules in its primary coordination sphere90.
3.3.2 Fluorescence Spectra
35
Each peak in the fluorescence spectrum represents a different Eu(III) ion

environment.
The fluorescence emission shifts to a lower wavenumber as water
molecules in the inner coordination sphere of the Eu(III) ion are removed due to the
formation of a coordination complex. The calculated ligand coordination number can be
calculated by the equation91:
CNL = 0.237 + 0.628
Eq. 3.17
where CNL is the total number of coordination bonds between the Eu(III) ion and ligand
or ligands and is the change in the fluorescence peak position relative to the 17276
cm-1 peak of the full hydrated Eu(III) ion. The coordination number of a ligand can be
calculated from the total coordination number if the speciation of the system is known.
The coordination numbers determined by this work have been reported with a relatively
large error, 0.5, to account for quenching effects by water molecules in outer hydration
spheres7.
3.4 Hypersensitivity Spectroscopy
The oscillator strength of integrated intensity, P, is defined by the equation92:

P = 4.3198E- 09 ( )d
i
Eq. 3.18
where is the molar absorptivity at the energy (cm-1). The integral can be calculated
by90:
( )d =
S
[M]c
Eq. 3.19
where S is the area of the hypersensitive transition spectrum in units of absorbancecm-1,

[M] is the total concentration of the Ln(III) ion in molarity and c is the path length of the
cell in cm. This substitution of Eq. 3.19 for the integral reduces Eq 3.18 to:
P=
(4.3198E 09)S
[M]c
Eq. 3.20
The value of S was determined by integration of the area of the hypersensitive transition
peak by a trapezoidal approximation method (GRAMS/32).
36
A plot of P versus the ligand to metal concentration ratio, Figure 4.1 and 4.2, can
be resolved into linear regions for systems in which the complexes are formed between
the ligands and a single metal ion and the ligands have a sufficiently high affinity for the
metal ion90. The first region can be defined by [L] : [M] < 1, limiting complexation to the
formation of the ML species. The second region can be defined by the formation of the
ML2 species, occurring when the values of the [L] : [M] ratio is between 1 and 2. The
ML3 and ML4 species, if present, should have linear ranges occurring when the [L] : [M]
ratio is between 2 and 3 and 3 and 4, respectively. A linear fit, Eq. 3.1, of P as a function
of the [L] : [M] ratio was performed where x = [L] : [M] ratio and y = P. The linear fit of
the first region was performed on [L] : [M] values between 0 and 0.7 to limit complex
formation to the ML species to avoid the influence of the ML2 species on the value of P.
The intercept of this linear fit is PM, the oscillator strength of the Ln(III) aqua ion.
Another linear fit was performed for the region where the [L] : [M] ratio was between 1.3
and 1.7, a range where the formation of the ML2 species should be the major species
formed. The value of the oscillator strength of the ML species, PML, was calculated from
the intersection of the linear regressions of ML and ML2 regions. The oscillator strength
of additional species can be calculated using this method with the linear regressions of
the appropriate regions. At some [L] : [M] ratio, P approaches a constant value which
indicates that the metal ion is not adding an additional ligand as the [L] : [M] ratio
continues to increase. This constant value can be treated as the oscillator strength of the
MLn species and n is the highest [L] : [M] integer ratio value where changes in P are still
observed.
3.5 NMR
The acid dissociation constants defined by the concentration of the species are
discussed in section 3.1. Acidic equilibria are typically much faster than the NMR time
scale, so the 1H NMR spectra would be expected to have peaks that are representative of
the weighted average of the concentrations of the acid and conjugate base forms of the
molecule. Acidic protons of a molecule rapidly exchange with the deuterium ions of
deuterium oxide so these proton environments should not have peaks that appear in 1H
37
NMR spectra.
The concentration acid dissociation constants in this study were
determined from the chemical shift change of the non-exchangeable protons (protons
covalently bonded to a carbon atom) caused by the acid/base equilibria of the molecule.
NMR techniques can not differentiate equilibria involving the carboxylic acid
groups in the 2 or the 6 positions of PDA and DPA because of the symmetry of these
molecules. Therefore, the values of the acid dissociation constants for the 2,6-carboxylic
acid groups for each ligand were reported as a single, average acid dissociation constant.
Because these experiments were performed in deuterium solvents, the deuterium
ion was substituted for the hydrogen ion in calculations of pcH. The value of pcD was
calculated using the equation93:
pcD = pHr + 0.40
Eq 3.21
where pcD is the log (deuterium ion concentration) and pHr is the meter reading from a
calibrated electrode. This equation accounts for the activity coefficient difference
between the different isotopes of the hydrogen ion and so the values of pKa calculated
with pcD and pcH should be approximately the same.
The acid dissociation constants were determined by analyzing the change in the
chemical shift of nonexchangable protons on the molecule versus pcD. The change in the
chemical shift was fitted using the Hendersen-Hasselbach equation94:
pcD= pKax + log
[Hx-1L]
[Hx L]
Eq. 3.22
where pKa is the negative log of the concentration acid dissociation constant, [HxL] and
[Hx-1L] are the concentrations of the acidic and basic forms of the molecule in units of
molarity and the species charges are not shown. Plots of the 1H NMR chemical shift
versus pcD for PDA and DPA are shown in Figures 4.21 and 4.22. The molecules are
undergoing acid equilibrium in the pcD regions of the plots where the chemical shift is
changing. The [Hn-1L] : [HnL] ratio was calculated from the change in the chemical shift
between the plateau regions using the equation:
[H n -1 L] A e
=
[H n L] e B
38
Eq. 3.23
where A is the value of the constant chemical shift of HnL at lower pcD than the
inflection region, B is the value of the constant chemical shift of Hn-1L at a higher pcD
than the inflection region and e is the chemical shift of the experimental point in the
inflection region between the plateaus of A and B. This reduces Eq. 3.22 to:
A e
pKax = pcD - log
e B
Eq. 3.24
The pKa values were calculated for each data point between the selected plateau areas for
each peak and then were averaged to obtain the peak pKa value. For peaks that showed a
change of chemical shift over the same range, the peak pKa values were averaged to
obtain the reported concentration acid dissociation constant.
3.5.2 Nuclear Overhauser Effect
The nuclear Overhauser effect (nOe) is a through-space coupling of the nuclear

dipoles of protons on a molecule. This dipole coupling can provide a mechanism for the
relaxation of an excited nuclide.
The coupling intensity can be described by the
equation95:
* 6
1
r
i (s) c
Eq. 3.25
where i(s) is the peak enhancement for the ith off-resonance peak caused by nOe when
the resonance peak has been completely saturated, * is a relaxation factor due to the
dipole interaction, c is the molecular correlation time and r is the distance between the
two nuclei. The values of * and c are assumed to be constant because the variations of
these paramaters are typically insignificant for different atoms on the same molecule95.
The value of for a peak was calculated from the integrated area of the off-resonance
and resonance peaks, shown by95:
I
A
=
I0
A0
39
Eq. 3.26
where I is the intensity of the peak, A is the area of the peak and the subscript denotes
values from the resonance peak. This leads to the relationship:
Ao
r6
A
Eq. 3.27
which allows a comparison of the ratio of the resonance and off-resonance peaks to the
distances between the proton environments those peaks represent.
3.6 Calorimetry
3.6.1 Change of Enthalpy
The speciation was controlled by using the ligand solution as the titrant, allowing
the step-wise formation of the ML complex followed by the ML2 shown in Eq. 3.10 and
3.11. The heat change produced by the formation of each complex species can be used to
calculate the change in enthalpy from the equation:
H n =
- qn
c
Eq. 3.28
where Hn is the change in enthalpy of the reaction in kJ/mole, qn is the heat per addition
in kJ/L, c is the concentration of the titrant in mole/L and the subscript n refers to the
formation of the first (n=1) or second (n=2) complex as given by Eq. 3.10 and 3.11. The
Hn value of each complex was calculated as the average from each titrant addition
corresponding to the [L] : [M] ratio for the desired species. Each titration was repeated
two or more times and the values were reported as the average of those experiments.
The heat of dilution was determined for each titrant and used as a background
correction factor for experiments performed with the same titrant and in the same pH and
ionic media. At the pH of these experiments, the predominant species of DPA and CA is
the monoprotonated form of the ligand. Upon complexation, this proton is displaced.
The change in enthalpy of protonation for the fully deprotonated ligand species was
experimentally determined and used to account for the change of heat caused by the
proton displacement. The error values of Hn were propagated using the statistical error
for the experimental heats and the errors associated with the heat of dilution and the heat
of protonation.
40
3.6.2 Change of Entropy
The value of the change in the Gibbs free energy was calculated by the equation:
Gn = -RT ln (Kn)
Eq. 3.31
where Gn is the change in the Gibbs free energy of the reaction in kJ/mole, Kn is the
equilibrium constant, the value of n is the number of ligands coordinating to the metal ion
in the complex species as given by Eq. 3.10 and 3.11, R is the gas constant in units of
J/moleK and T is the temperature in Kelvin. The change in entropy can be calculated by
the equation:
Gn = Hn TSn
Eq. 3.32
where Sn is the change of the entropy of the reaction in J/mole K. The error of Sn was
propagated from the errors associated with the values of Gn and Hn.
41
CHAPTER 4
RESULTS
4.1 Acid Dissociation Constants

The concentration acid dissociation constants of PDA, DPA and CA were
determined by potentiometric titration at 25.0 0.1C and 0.10, 0.50 and 2.00 M sodium
perchlorate media and are listed in Tables 4.1, 4.2 and 4.3, respectively. The values were
calculated using PSEQUAD as explained in section 3.2 by fitting the pH profile of 20 to
40 titrations of each ligand. All ligands were fit with a triprotic chemical model (Eq. 3.3,
3.4 and 3.5). The third deprotonation of DPA can be neglected under the conditions of
this work because the proton is completely dissociated in the initial solution because of
its highly acidic nature (pKa < 1).
The PSEQUAD fits produced using a triprotic
chemical model have high correlation coefficients for each ligand system, indicating that
the model is appropriate for fitting the data. There was a large relative error associated
with the pKa3 values of PDA and CA and the pKa2 value of DPA. This error can be
attributed to the pKa values being obtained from solutions in which the pH are outside of
the linear range of a glass electrode1. The other pKa values have relative errors of less
than 2%.
The acid dissociation constants of PDA and DPA were also measured by 1H NMR
(Tables 4.1 and 4.2). The values are from multiple titrations and are calculated from over
100 data points at 25.0 0.1C in 0.50 M sodium perchlorate media. The pKa values of
42
the 2, 6-carboxylic acid groups of PDA and DPA were reported as an average value as
discussed in section 3.5.A. The values have relative errors less than 9% and are within
one standard deviation of the pKa values determined by potentiometry.
4.2 Lanthanide(III) Stability Constants
The lanthanide(III) stability constants of DPA and CA, Table 4.4 and 4.5, were
determined by potentiometric titration at 25.0 0.1C. The Ln(III)-DPA system was
studied in 0.50 and 2.00 M sodium perchlorate media while the Ln(III)-CA system was
studied in 0.10, 0.50 and 2.00 M sodium perchlorate media. The values were calculated
using PSEQUAD, as explained in section 3.2, by fitting the pH profile of between 10 and
30 titrations of each lanthanide(III) ligand system. The pH profiles of the lanthanide(III)
complexes were fit with a chemical model that assumed all protons were displaced upon
coordination using the concentration acid dissociation constants determined by this study.
The model allows for the stepwise formation of ML and ML2 species as shown by Eq.
3.10 and 3.11.
The concentration of the ligand was never greater than twice the
lanthanide(III) ion concentration so a ML3 species was not included in the fit. DPA was
not expected to form a ML3 complex with lanthanide(III) ions due to the number of
coordination sites the ligand can occupy and the steric bulk of the ligand. CA can
potentially form a ML3 species with lanthanide(III) ions but the stability constant of this
complex was not determined since the results are to be compared with IDA which does
not form a ML3 complex2. All fits produced high correlation coefficients that indicate the
selected model was appropriate for fitting the data.
The lanthanide(III) stability constants of PDA could not be determined by
potentiometry as the changes in acidity profile of the ligand and the complex were
negligible.
4.3 Calorimetry
The change in enthalpy was calculated from experimental heats using Eq. 3.28.
The change of Gibbs free energy was calculated from the corresponding equilibrium
constant of the reaction using Eq. 3.31. The change of entropy was calculated from H
and G values for the reaction using Eq. 3.32.
43
The complexation titrations were performed at 25.000 0.001C in pH 5.3 to 5.5,

0.100 M MES and 0.50 M sodium perchlorate. The DPA and CA are predominantly the
monoprotonated species at this pH.
The change in enthalpy and entropy for the
deprotonation of the ligands were determined by titration at a pH equal to the highest pKa
value with a known acid and used to correct for the deprotonation which occurs upon
complexation. The titrations of each ligand were performed under the same temperature
and ionic media conditions as complexation experiments. The values of H and S were
calculated as the average of three titrations and were determined to be 8.36 0.64 kJ
mol-1 and 157.4 2.2 J mol-1 K-1 for DPA and 23.7 1.1 kJ mol-1 and 127.3 3.8 J mol1
K-1 for CA. The heat of complexation of PDA could never be distinguished from the
heat of dilution. The G, H and S values of complexation CA and DPA formation are
shown in Table 4.6 and Table 4.7.
Representative spectra of the 4I9/2 2G7/2, 4G5/2 transition of Nd(III) and of the
5
I8 5F1, 5G6 transition of Ho(III) are shown in Figures A.1 and A.2. Upon complex
formation, the shape of the peak changes and the area of the absorbance peak increases as
a result of the hypersensitivity of the metal ion. The use of 10 cm path length cells
allows the measurement of mM concentrations of the hypersensitive region of the Nd(III)
and Ho(III) spectra with high reproducibility. The area of the peak can be used to
calculate the oscillator strength, P, as defined in Eq. 3.17.
4.4.1 PDA
Little change is observed in the area and shape of the Nd(III) (Figure A.3) or
Ho(III) (Figure A.4) hypersensitive spectra upon increasing the concentration of PDA.
As the [L] : [M] ratio changes from 0 to 0.8 at pH ~5.5, the oscillator strength of Nd(III)
(Table A.1) changes by less than 5% and the oscillator strength of Ho(III) (Table A.2)
increases by less than 9%. Similar change was seen when the PDA was present in two
and three fold excess, indicating that PDA formed only a relatively weak complex with
Nd(III) and Ho(III) ions.
4.4.2 DPA and CA
44
A significant change occurs in the shape and area of the peak of the Nd(III)
spectrum upon the addition of DPA (Figure A.5). The oscillator strength has a large
increase (~30%) when the [L] : [M] ratio increases to 1.0, Table A.3. Similar changes are
seen in the spectra of Ho(III) as DPA was added, Figure A.6 and Table A.4. The changes
in the peak shape and the increase of the oscillator strength are indications of strong
complex formation.
Significant changes in the shape and area of the peak of the Nd(III) and Ho(III)
hypersensitive spectra (Figure A.7 and A.8) are observed as the CA concentration
increases. The oscillator strength shows a large increase (~30%) as the [L] : [M] ratio
approaches 1.0, listed in Tables A.5 and A.6, and indicates strong complex formation.
The degree of complexation of DPA with Nd(III) or Ho(III) shows a dependence
on pH when varied between 2.1 and 5.2 as can be seen in the representative Ho(III)
spectra shown for conditions favoring ML species (Figure A.9) and ML2 species (Figure
A.10. The change of the oscillator strength between the values at pH 3 and pH 5 is larger
for the ML2 species (P = 1.8) versus the ML species (P = 0.8), indicating that
formation of the second complex is more sensitive to pH. The oscillator strengths are
nearly constant for both the ML and ML2 species between pH 4.5 and 5.5, indicating that
the different pH values had only a minimal effect in the experiments used to determine
complex oscillator strength values.
The complexes of CA show similar trends for Nd(III) and Ho(III), exhibiting a
minimal pH dependence over a range from 2.3 and 5.5 as shown in a representative set of
Nd(III) spectra, Figure A.11.
The oscillator strength values, Table A.9, show no
significant change over this pH range. The ML2 species of CA complexes with Nd(III)
and Ho(III) are more sensitive to pH as shown in the Nd(III) spectra, Figure A.12. The
experiments used to determine the complex oscillator strength values are not expected to
show a significant pH effect for either species under the conditions of this work.
The initial ligand solutions for the hypersensitive spectroscopy experiments were
prepared at pH ~5.0. The ligands are predominatly the monoprotonated species at this
pH. Upon addition of the metal ion, the pH showed a sharp decrease of several units for
DPA and CA but did not measurably change for PDA. This indicated that DPA and CA
45
are completely deprotonated when forming complexes with lanthanide(III) ion under
these conditions. The lack of pH change for PDA samples indicates that either only a
minor amount of complexation occurs or that any PDA complex that forms does not
dissociate the proton of the HPDA-1 species.
4.4.3 Oscillator Strengths
The experimental oscillator strengths of the Nd(III) complexes plotted against [L]
: [M] for both DPA and CA are shown in Figure 4.1. The change of P indicates the
stepwise formation of ML and ML2 complexes of DPA with Nd(III) as seen in the
separate linear regions of the plot discussed in section 3.4. The constant P seen after [L] :
[M] exceeds 2.50 indicates no higher order complexation is occurring. The change of P
of the CA complexes as the [L] : [M] ratio increases indicates stepwise complexation of
CA, forming ML, ML2 and ML3 species (Figure 4.1). All of the linear fits of have a high
correlation coefficient, Table 4.8, except the [Nd(DPA)2] region.
The experimental oscillator strengths of Ho(III) are plotted against [L] : [M],
Figure 4.2, for both DPA and CA. The change of P in the plot indicates the stepwise
formation of ML and ML2 complexes of DPA with Ho(III) and CA with Ho(III). The
oscillator strength becomes constant after the [L] : [M] ratio exceeds 2.00 for both DPA
and CA systems, indicating no further complexation is occurring.
Linear fits of each
species region are shown in Table 4.9 and have high correlation coefficients. Ho(III)-CA
spectra and oscillator strengths that have been published from the work are shown in
Appendix E.
Because the oscillator strength values of the PDA complex did not change
significantly, PDA was not analyzed. The oscillator strengths of the M, ML and ML2
species, Table 4.10, were calculated as discussed in section 3.4. The values of the
oscillator strengths determined for the free metal ions from both DPA and CA
experiments show good agreement. The PML3 value for Nd(III) complexes of CA were
not determined due to the limited solubility of the ligand and the extinction coefficient of
the Nd(III) ion which restricted the [L] : [M] range that could be studied.
4.5 Eu(III) Laser Fluorescence
4.5.1 Excitation Spectra
46
The number of peaks corresponds to the number of distinguishable environments

of the Eu(III) ion in the 7F0 5D0 selective excitation spectrum3. The intensities of
different sets of spectra cannot be directly compared because different amplification
settings were used during the collection of different data sets to adjust to the much
weaker intensities of the highly hydrated Eu(III)3. The relative intensities of different
data sets are not important since this work focused on the determination of the peak
positions and the measurement of the fluorescent decay lifetime of the peak.
The
excitation spectrum of europium perchlorate had one very weak peak centered at 17276
cm-1, Figure B.1, which is assumed to be the [Eu(H2O)9]3+ species. The experiments
were performed at 23 1C in 2.00 M sodium perchlorate media.
4.5.2 PDA
Representative spectra of the 7F0 5D0 selective excitation of Eu(III) in solutions
of varying PDA concentration are shown in Figure B.2 with arbitrary units of intensity.
A single, very weak peak was seen as the ratio [PDA] : [Eu(III)] was varied between 0.1
and 5.0 (Table B.1) at pH ~5.5. The peak, 17273 cm-1, corresponds to CNL = 1.3 0.5,
calculated by Eq. 3.17 as discussed in section 3.3.2. This coordination number value
indicates that the probable species is [Eu(HxPDA)(H2O)8]1+x with PDA coordinating as a
monodentate ligand and x equal to 0 or 1, Table 4.11. The weak intensity of the peak at
17273 cm-1 prohibited lifetime measurements with PDA.
4.5.3 DPA
Representative spectra of the 7F0 5D0 selective excitation of Eu(III) during a
titration with DPA are shown in Figure B.3 with arbitrary units of intensity. The peaks
and concentrations are listed in Table B.2. When [DPA] < [Eu(III)], a single peak is
observed in the spectra at 17260 cm-1. This peak has a shoulder at 17252 cm-1 that could
not be isolated and maintained a constant intensity of approximately 10% relative to the
intensity of the 17260 cm-1 peak. The peaks of Eu(III) excitation spectra are sharp and
can be fit as Lorentzian lineshapes so the shoulder must be considered as an additional
Eu(III) environment4. The peak and the shoulder have CNL = 4.4 0.5 and 6.6 0.5,
Table 4.11. Because the shoulder could not be resolved from the peak using different pH
and concentration ratios and was always present in a fixed ratio relative to the peak, the
47
species that the shoulder and peak represent must be related. Therefore, the number of
water molecules in the inner hydration sphere of 3.9 0.5, nH2O calculated by Eq. 3.16,
for the peak and shoulder is reported as an average of both species.
The peak
corresponds to the ML complex where DPA is coordinating in a tetradentate manner,

corresponding to a [Eu(DPA)(H2O)4] species (Table 4.11). The shoulder is probably a
different geometrical form(s) of the tetradentate coordinating DPA species, probably
involving
some
geometric
isomerization
of
the
ligand
corresponding
to
[Eu(DPA)(H2O)3] species (Table 4.11). DPA can undergo ring isomerization similar to
cyclohexane and has several variations such as boat and chair forms.
Molecular
modeling performed by Dr. Kenneth L. Nash at Argonne National Laboratory with the
Alchemy program indicates that both the boat and chair forms should displace 4 to 5
water molecules upon coordination. The seemingly higher coordination number of the
shoulder represents the intermediate as the molecule converted between boat and chair
forms since the modeling indicates that the intermediate form could displace 1 to 2
additional water molecules.
Another peak is observed at 17239 cm-1 when the DPA concentration exceeds that
of the Eu(III) ion. This peak has CNL = 9.2 0.5 and nH2O = 1.5 0.5 and corresponds to
the ML2 species where two DPA molecules coordinate the Eu(III) ion in a tetradentate
fashion, [Eu(DPA)2(H2O)]3- (Table 4.11).
4.5.4 CA
Representative spectra of the 7F0 5D0 selective excitation of Eu(III) during a
titration by CA are shown in Figure B.4 with arbitrary units of intensity with the total
concentrations of each reagent are listed in Table B.3. An initial peak forms at 17266
cm
-1
in the spectra when [CA] < [Eu(III)]. The values of CNL = 3.2 0.5 and nH2O =
4.5 0.5 indicate that the predominant species is [Eu(CA)(H2O)4,5]+ (Table 4.11). A
second peak appears at 17252 cm-1 when the CA concentration exceeds the concentration
of Eu(III) ion. The values of CNL = 6.6 0.5 and nH2O = 2.9 0.5 of this peak are
consistent with tridentate complexation by two CA molecules to the metal ion,
corresponding to a [Eu(CA)2(H2O)3]- species (Table 4.11).
48
A third peak was observed at 17233 cm-1 when the CA concentration was several
times in excess of the metal ion. The peak was not observed at an intensity that would
allow the measurement of the fluorescence decay lifetime. The peak has a CNL = 10.8
0.5, corresponding to the [Eu(CA)3]3- species (Table 4.11). Eu(III)-CA flourescence
spectra, waters of hydration and calculated coordination numbers that have been
published from the work are shown in Appendix E.
4.6 NMR
Typical 1H NMR spectra of PDA and DPA are shown in Figures C.1 and C.2,
respectively.
Plots of the change in chemical shift of nonexchangable protons versus pD are
shown in Figures 4.3 and 4.4 for PDA and DPA. The acid dissociation constants were
determined from the change of the chemical shift of the peak as pD was varied using Eq.
3.20 as discussed in section 3.5.A. The calculated acid dissociation constants are listed in
Tables 4.1 and 4.2 and have been discussed in section 4.1.
4.6.2 1H NMR Peak Identification of PDA
The peaks in the spectrum shown in Figure C.1 can be attributed to the different
proton environments of PDA. The nOe experimental results are shown in Table 4.12
with the different proton position assignments shown in Figure 4.5. The proton bonded
to the carbon in the alpha position from the amine appears as a doublet of doublets with a
chemical shift between 4.1 and 3.1, depending on pD, and shown as Ha in Figure 4.23.
This peak appears at chemical shifts typical of protons in proximity to amine and
carboxyl functional groups and with the expected multiplicity.
The integration value of the peak located at 1.7 to 1.2, depending on pD,
corresponds to 2 protons. The homonuclear decoupling of this peak affects the splitting
pattern of all other peaks. The decoupling of the proton alpha to the amine results in
significant change in the multiplicity of the 1.7 ppm peak and only a small change in the
2.4 ppm peak. This indicates that this peak could be assigned to the protons bonded to
the carbon in the beta position from the amine, shown as Hb in Figure 4.5. The nOe
results in Table 4.12 supported this assignment of the proton.
49
A symmetric doublet of doublets appears in the spectra at 2.4 and 2.1 ppm in
acidic systems. These peaks merge as the acidity decreases, forming a single peak at 1.9
ppm as pD approaches 10.0. Both doublets show strong coupling with the peak at 1.7
ppm while the peak at 2.4 ppm shows coupling to Ha proton. This indicates that this
peak system represents the protons bonded to the carbon in the para position from the
amine. The proton environment is split by the geometry of the molecule with one of the
protons having a significantly higher interaction with the carboxylic acids when it is in
the axial position, shown as Hc in Figure 4.5, and corresponds to the peak at 2.4 ppm in
acidic systems. The interaction of the Hd proton is weaker with the carboxylic acid
groups and so a lower chemical shift, 2.1 ppm, is observed. The peaks merge in less
acidic systems because the carboxy groups orient equatorially because of the charge
repsulion, limiting the carboxy-Hc interaction.
4.6.3 1H NMR Peak Identification of DPA
The peaks in the spectrum shown in Figure C.2 can be attributed to the different
proton environments of DPA shown in Figure 4.6. The nOe experimental results are
shown in Table 4.13. The proton bonded to the carbon alpha to the amine, Ha in Figure
4.6, appears as the peak between 4.4 to 3.5 ppm, depending on pD. The peak from 4.2 to
3.2 ppm, depending on pD, is due to the proton of the N-acetate group shown as Hf in
Figure 4.6. Both peaks appear in predictable regions for protons in proximity to amine
and carboxyl functional groups and have the expected splitting patterns and integration
values.
The integration value of the peak between 2.0 to 1.4 ppm, depending on pH,
corresponds to 2 protons. The homonuclear decoupling of this peak affects all proton
peaks except the Hf proton peak but only shows a change in multiplicity when the proton
alpha to the amine is decoupled. This indicates that the peak corresponds to the protons
bonded to the carbon in the beta position relative to the amine, shown as Hb in Figure
4.6. The nOe indicates that this is the correct assignment of the proton positions on the
structure but the nOe results are not as simple as might be expected. The complication of
the nOe spectra is due to multiple geometries of the ring structure as well as the addition
of different splitting caused by protons on the varying sides of the ring.
50
The multiplet peaks between 2.3 to 1.85 ppm and 1.8 to 1.7 ppm, depending on
pD, each integrate to the equivalent of 1 proton. The homonuclear decoupling of these
peaks induces changes in the Hb proton peak. The peak at 2.3 ppm also affects the peak
from the protons at Ha in acidic systems, indicating that these protons are bonded to the
carbon in the para position relative to the amine. The proton Hc corresponds to the peak
at 2.3 ppm, having an increased interaction with the carboxylic acid groups. The peak at
1.8 ppm is least affected by changes in pH and can be assigned to Hd, seen in Figure 4.6.
The nOe results in acidic systems in Table 4.13 are consistent with these proton
assignments.
4.6.4 NMR of Lanthanide(III) Complexes
A series of 1H NMR spectra of PDA were taken for solutions of Eu(III) at 25.0
0.1C and 0.5 M ionic strength. The pHs, 3.4, 1.9 and 0.6, were chosen as conditions that
should show a range of complex formation from some Eu(III)-PDA complexation at pH
3.4 to very little interaction at pH 0.6. The spectra should show a large shift and
broadening of the peaks in the NMR spectrum upon the complexation due to the
paramagnetic Eu(III) ion. Only a small change is observed in the chemical shifts of the
peaks that corresponds to acidity effects upon the ligand. Only a small broadening is
observed, indicating that either only a minimal interaction occurs between the Eu(III) ion
and PDA or that the exchange rate of the complex is faster than the NMR time scale with
the ligand predominantly residing in the uncomplexed form.
Spectra of the La(III) and Lu(III) complexes of DPA were studied using 1H NMR.
The peaks in the spectrum of the La(III) complexes are very broad (Figure C.3),
indicating that the ligand is involved in a chemical equilibrium with kinetics on the NMR
time scale. The broadness of the peaks makes comparisons between the [La(III)DPA]
spectrum and the DPA spectrum difficult. The peaks in the spectra of the Lu(III)-DPA
complexes remain sharp and maintain their multiplicity. Both the chemical shift and the
multiplicity of the peaks change upon the formation of the [Lu(III)DPA] complexes
(Figure C.4). Many additional peaks are observed in the spectrum of a solution with a
molar ratio of DPA twice that of Lu(III) (Figure C.5). Some of the peaks are similar to
the ones from the [Lu(III)DPA] and DPA solutions but a series of additional peaks is also
51
observed. The peaks that are similar to DPA indicate that the uncomplexed ligand is
present. The additional peaks indicate that the DPA ligands do not complex Lu(III)
symmetrically. One of the DPA molecules in the ML2 complex is in a geometrically
similar form to the DPA molecule in the ML species while the other DPA molecule exists
in some other chemical or geometrical form.
The La(III) and Lu(III) complexes of CA were studied using 1H decoupled
13
NMR. The spectra of CA consist of peaks at 118.3, 153.9, 175.9 and 176.5 ppm. These
peaks, based on typical functional group chemical shifts of 13C NMR, can be assigned to
the C3, C2, C1 and C1A carbon as shown on the structure in Figure 4.7. The carboxyl
carbon atoms are highly insensitive in 13C NMR experiments and require a significantly
higher number of data acquisitions5. The position of the carboxylic acid chemical shift
does not change significantly when bonded to an ethylene or aromatic carbon and so will
not give additional information on the resonance form of the CA. Therefore, the spectra
were not collected over adequate times to determine the chemical shift of the carboxylic
acids. The spectrum of La(III)-CA has peaks at 117.4, 155.4, 171.2 and 176.2 ppm,
having a significant change in the C1 or C1A carbon atoms. The spectrum of Lu(III)-CA
has peaks at 120.0, 147.4, 169.1 and 185.6 ppm. Most of the peaks did not show
significant change upon formation of the complex. Because the aromatic and alkene
region significantly overlap in
13
C NMR, it is not possible to determine if one of the
resonance forms of CA was preferred upon coordination to the lanthanide(III) ions. The
two carbon atoms ortho to the amine show a significantly change in their chemical shift.
The chemical shifts of the other peaks show an increased separation of the positions in
the complexed forms when compared to the free ligand. This can be explained by
nonsymmertical coordination where the metal ion favors coordination with one
carboxylate group instead of equally coordinating to both groups. This effect would
increase in Lu(III) complexes when compared to La(III) because of the smaller ion size,
as is observed. Because of the low solubility of CA and the relative insensitivity of 13C
NMR, exceedingly long periods were required for data collection required and so further
experiments were not performed.
4.7 Crystallography
52
The crystal structures of PDA and DPA were determined with a high correlation
of fit. The structure of PDA is shown in Figure D.1 with structure parameters shown in
Tables D.1, D.2, D.3, D.4 and D.5. The structure of DPA is shown in Figure D.2 with
structure parameters shown in Tables D.6, D.7, D.8, D.9 and D.10.
53
Table 4.1.
The concentration acid dissociation constants for PDA, T = 25.0C, NaClO4 media.
Ionic Strength (M)
Method
log Ka1
log Ka2
log Ka3
0.10
potentiometry
10.39 0.05
3.46 0.04
1.7 0.3
potentiometry
10.51 0.03
4.17 0.02
1.9 0.3
NMR
10.52 0.06
potentiometry
10.84 0.07
0.50
2.00
54
2.74 0.24
4.09 0.05
1.8 0.3
Table 4.2.
The concentration acid dissociation constants for DPA, T = 25.0C, NaClO4 media.
Ionic Strength (M)
Method
log Ka1
log Ka2
log Ka3
0.10
potentiometry
9.42 0.05
2.98 0.05
1.4 0.3
potentiometry
9.69 0.03
3.02 0.04
1.1 0.3
NMR
9.78 0.18
potentiometry
9.55 0.01
0.50
2.00
55
2.07 0.08
3.14 0.02
1.1 0.3
Table 4.3.
The concentration acid dissociation constants* for CA, T = 25.0C, NaClO4 media.
Ionic Strength (M)
log Ka1
log Ka2
log Ka3
0.10
10.75 0.04
3.02 0.06
1.3 0.3
0.50
10.81 0.05
3.47 0.06
1.0 0.3
2.00
10.45 0.02
3.27 0.03
1.0 0.3
* Determined by potentiometry.
56
Table 4.4.
Stability constants of select lanthanide(III) ions with DPA, T = 25.0 C NaClO4 media.
*
La
Nd
Eu
Ho
Lu
Ionic Strength (M)
log 1
log 2
0.50
9.73 0.20
17.98 0.22
2.00
9.38 0.25
16.72 0.26
0.50
10.58 0.60
20.59 0.40
2.00
10.18 0.56
19.90 0.50
0.50
10.87 0.19
19.56 0.19
2.00
10.57 0.16
19.09 0.16
0.50
9.54 0.04
15.15 0.05
2.00
10.70 0.13
16.77 0.16
0.50
10.18 0.08
16.15 0.10
2.00
12.09 0.36
21.62 0.40
57
Table 4.5.
Stability constants of select lanthanide(III) ions with CA, T = 25.0 C, NaClO4 media.
*
La
Nd
Eu
Ho
Lu
Ionic Strength (M)
log 1
log 2
0.10
7.37 0.19
14.74 0.22
0.50
6.92 0.12
14.24 0.13
2.00
7.36 0.13
13.63 0.83
0.10
7.50 0.17
14.66 0.43
0.50
6.83 0.34
14.75 0.14
2.00
7.71 0.21
15.38 0.20
0.10
7.67 0.18
14.75 0.54
0.50
6.47 0.64
14.81 0.11
2.00
7.49 0.13
14.53 0.25
0.10
7.82 0.07
15.23 0.12
0.50
7.19 0.27
15.28 0.15
2.00
7.20 0.21
14.88 0.21
0.10
9.20 0.18
16.28 0.71
0.50
7.18 0.15
14.97 0.07
2.00
7.82 0.11
15.23 0.14
58
Table 4.6.
Thermodynamic values for the DPA complexation with Ho(III) or Nd(III), pH = 5.30 to
5.50, [MES] = 0.100 M, T = 25.000C, I = 0.50 M NaClO4.
Ln(III)
Ho(III)
Nd(III)
Gn (kJ mole-1)*
Hn (kJ mole-1)
Sn (J mole-1 K-1)
-54.46 0.10
11.5 2.9
221 10
-32.02 0.12
0.6 3.1
109 10
-60.4 1.5
11.8 3.0
242 11
-57.14 0.99
1.0 3.3
203 11
* Calculated from the equilibrium constant.
59
Table 4.7.
Thermodynamic values for the CA complexation with Ho(III) or Nd(III), pH = 5.30 to
5.50, [MES] = 0.100 M, T = 25.000C, I = 0.50 M NaClO4.
Ln(III)
Ho(III)
Nd(III)
Gn (kJ mole-1)*
Hn (kJ mole-1)
Sn (J mole-1 K-1)
-41.04 0.67
20.1 3.8
205 13
-46.18 0.37
16.6 3.9
211 13
-38.99 0.84
14.7 3.8
180 13
-45.21 0.35
15.9 3.9
165 13
* Calculated from the equilibrium constant.
60
26
[Nd(CA)3]
24
22
P(x106)
20
[Nd(CA)2]
18
16
14
[NdCA]
12
[Nd(DPA)2]
10
[NdDPA]
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
[L] : [M]
Figure 4.1.
The oscillator strength of Nd(III) complexes plotted versus the ligand to metal
concentration ratio, I = 2.00 M NaClO4, pH = 4.50 - 6.00, T = 23C.
61
Table 4.8.
Values from the linear regressions of Figure 4.1 for the change of the oscillator strength
of Nd(III) when complexed with DPA and CA, I = 2.00 M NaClO4, pH = 4.50 - 6.00, T =
23C.
complex
slope
intercept
correlation coefficient
NdCA
4.76 0.12
9.53 0.07
0.984
Nd(CA)2
3.59 0.15
10.86 0.29
0.976
Nd(CA)3
0.83 0.12
20.61 0.53
0.980
NdDPA
3.11 0.12
9.47 0.66
0.951
Nd(DPA)2
0.56 0.13
12.36 0.20
0.588
62
24
[Ho(CA)2]
22
20
P(x106)
18
16
14
12
[HoCA]
[Ho(DPA)2]
10
8
[HoDPA]
6
0.00
0.25
0.50
0.75
1.00
1.25
1.50
1.75
2.00
2.25
2.50
2.75
[L] : [M]
Figure 4.2.
The oscillator strength of Ho(III) complexes plotted versus the ligand to metal
concentration ratio, I = 2.00 M NaClO4, pH = 4.50 - 6.00, T = 23C.
63
Table 4.9.
Values from the linear regressions of Figure 4.2 for the change of the oscillator strength
of Ho(III) when complexed with DPA and CA, I = 2.00 M NaClO4, pH = 4.50 - 6.00, T =
23C.
complex
slope
intercept
correlation coefficient
HoCA
7.79 0.10
5.92 0.05
0.996
Ho(CA)2
8.24 0.25
5.56 0.36
0.994
HoDPA
4.64 0.22
6.20 0.12
0.954
Ho(DPA)2
4.20 0.41
6.65 0.60
0.904
64
Table 4.10.
The oscillator strengths of Nd(III) and Ho(III) and their complexes with DPA and CA*, I
= 2.00 M NaClO4, T= 23C.
system
PM / 106
PML / 106
PML2 / 106
Nd(III) DPA
9.47 0.66
12.98 0.12
14.51 0.04
Ho(III) DPA
6.20 0.12
10.94 0.39
15.26 0.12
Nd(III) CA
9.53 0.07
14.46 0.18
22.89 0.42
Ho(III) CA
5.95 0.05
12.15 0.21
23.26 0.05
* The subscript of P indicates the metal ion species.
65
Table 4.11.
Summary of the peaks observed by fluorescence peaks of Eu(III) for the various PDA,
DPA and CA, I = 0.50 and 2.00 M NaClO4, T = 23C.
system
peak (cm-1)
CNL
nH2O
probable species
Eu
17276
9.0 0.5
[Eu(H20)9]3+
PDA
17273
1.3 0.5
17260
4.4 0.5
17252
6.6 0.5
17239
9.2 0.5
1.6 0.5
[Eu(DPA)2(H20)]3-
17266
3.2 0.5
4.5 0.5
[Eu(CA)(H20)4]+
17252
6.6 0.5
2.9 0.5
[Eu(CA)2(H20)3]-
17233
10.8 0.5
DPA
CA
66
[Eu(PDA)(H20)8]+
3.9 0.5
[Eu(DPA)(H20)4]
[Eu(DPA)(H20)3]
[Eu(CA)3]3-
chemical shift (ppm)
4.00
3.75
3.50
3.25
3.00
2.75
2.50
2.25
2.00
1.75
1.50
1.25
Ha
Hc
Hd
Hb
7
pD
10 11 12 13
Figure 4.3.
The chemical shift of the peaks in the 1H NMR spectrum of PDA versus log of
concentration of the deuterium ion, I = 0.50 M NaClO4 and T = 25.0C. The peak legend
refers to proton assignments given in Figure 4.5.
67
4.5
chemical shift (ppm)
4.0
Ha
Hf
Hc
Hb
Hd
3.5
3.0
2.5
2.0
1.5
7 8
pD
10 11 12 13 14
Figure 4.4.
The chemical shift of various peaks in the 1H NMR spectrum of DPA versus log of
concentration of the deuterium ion, I = 0.50 M NaClO4 and T = 25.0C. The peak legend
refers to proton assignments given in Figure 4.6.
68
Table 4.12.
The nuclear Overhauser effect of PDA* at different pH, I = 0.50 M NaClO4 and T =
25.0C.
pH 0.30
peak (ppm)
4.20
2.40
2.10
1.70
IP
3.35
2.73
7.79
IP
0.32
34.0
IP
41.61
5.57
20.06
12.14
IP
pH 10.05
peak (ppm)
3.00
1.85
1.45
1.15
IP
3.93
2.99
spt
4.54
IP
13.50
20.05
13.44
42.60
IP
spt
0.85
36.61
spt
IP
* Values are reported as the ratio of the absolute value of the irradiated peak area divided
by the enhanced peak area. The symbol IP indicates the peak was the irradiation peak
of the nOe experiment. The symbol spt indicates selective population transfer occurred
at the peak during the nOe experiment.
69
H
H
O
OD
OD
D N
N
OD D D
Ha
H
H
OD
Hc
O
OD
Ha
Hb
Hd
Hb
Ha
Hd
Hb
Figure 4.5.
PDA proton atom designations used with 1H NMR.
70
Hc
Hb
D N
Hb
Hb
Ha
OD
O
Hb
Hb
Table 4.13.
The observed nuclear Overhauser effect of DPA* at different pH, I = 0.50 NaClO4 and T
= 25.0C.
pH 0.86
peak (ppm)
4.3
4.2
2.3
2.0
1.7
IP
54.2
59.2
51.9
58.9
IP
55.2
67.0
IP
80.6
56.1
50.4
58.9
79.6
IP
61.0
76.1
65.9
74.5
IP
4.0
3.8
2.2
2.0
1.7
IP
56.3
59.2
45.3
45.0
65.0
IP
68.8
19.0
IP
77.4
60.2
67.8
44.3
IP
75.2
59.3
58.8
76.2
IP
spt
62.7
spt
IP
pH 3.20
peak (ppm)
56.7
pH 14.10
peak (ppm)
3.5
3.2
1.85
1.75
1.45/1.35
IP
53.7
59.6
54.4
63.7
IP
69.3
IP
83.8(broad)
IP
82.3(broad)
81.6
63.8
IP(1.45)
54.9
81.9
65.2
IP(1.45)
58.0
78.6
67.9
IP(1.35)
* Values are reported as the ratio of the absolute value of the irradiated peak area divided
by the enhanced peak area. The symbol IP indicates the peak was the irradiation peak
of the nOe experiment. The symbol spt indicates selective population transfer occurred
at the peak during the nOe experiment.
71
H H
H
H
O
N D
H
H
H O
OD
OD
OD
OD
O
Ha
D N
DO
Hc
OD
Ha
Hf
Hf
OD
Hb
Hd
Hb
Ha
Hd
Hf O
OD
Hf
Hb
Figure 4.6.
DPA proton atom designations used with 1H NMR.
72
Hc
Hb
D N
Hb
Hb
Ha
OD
Hb
Hb
OD
H
C2
O
C1
OD
C3
H
C2
C1 A
Figure 4.7.
CA carbon atom designation used with 13C NMR.
73
O
OD
CHAPTER 5
DISCUSSION
5.1 Acid Dissociation Constants

The pKa2 value determined for PDA, 3.46 0.04, disagrees with the values
reported in the literature (Table 5.1). The value reported in the literature was fit with a
diprotic acid model. The potentiometric data from this study was analyzed using both a
diprotic model and a triprotic model of PDA to examine the effect on the second acid
dissociation constant value. The first and second pKa values of the triprotic model agree
with values determined using the diprotic model within 2 standard deviations. The
H3PDA+1 molecule is a minor species under the conditions of the potentiometric study
and so the inclusion of this proton results in only a minor change in the data fitting. The
literature pKa2 value is similar to the value determined by 1H NMR titrations, 2.74
0.24, which is the average of the second and third acid dissociation constant values as
discussed in section 4.1. PDA is an analog of iminodiacetic acid (IDA) which has three
reported pKa values (Table 5.2). The similarity between the acid dissociation constants
of nitrilotriacetic acid (NTA) and its analog DPA, discussed in the following paragraph,
would suggest that IDA and PDA should also have similar acidic behavior and would
support the use of a triprotic model for PDA. The difference of pKa2 values of PDA and
IDA is caused by the additional electron donating aliphatic groups of the piperidine
ring100.
74
The pKa1 and pKa3 values, 9.42 0.05 and 1.4 0.3, respectively, determined for
DPA are within 2 standard deviations of the values reported in the literature (Table 5.1).
The pKa2 value of DPA determined in this study was slightly higher than the value
reported in the literature, 2.98 0.05 versus 2.71. The difference may be due to the ionic
media of the two studies, potassium nitrate versus sodium perchlorate ionic of this work.
The acid dissociation constant values determined for CA, 10.75 0.04, 3.02
0.06 and 1.3 0.3 in 0.1 M sodium perchlorate, are within 2 standard deviations of the
previously determined values (Table 5.1). A direct comparison is difficult due to the
different ionic media and temperatures in the different studies. The pKa values of
dipicolinic acid (Table 5.2) are significantly different from those of CA despite the
structural similarity. The pKa1 value of CA more closely resembles the value listed for 4hydroxybenzene (Table 5.1), indicating that the acidity of the CA amine is strongly
affected by the phenolic resonance form.
5.2 Lanthanide(III) Stability Constants
5.2.1 PDA
The stability constants of PDA and lanthanide(III) ions could not be determined
from potentiometry as discussed previously in section 4.2. The values reported in the
literature (Tables 5.3 and 5.4) indicate that a moderately strong complex forms with
lanthanide(III) ions; these values are similar to the values reported for IDA, listed in
Table 5.5. The discrepancies of the values from this work and those in the literature are
discussed in section 5.8.1.
5.2.2 DPA
The previously determined lanthanide(III) stability constants of DPA are listed in
Tables 5.3 and 5.4. The stability constants values of DPA have a similar trend across the
lanthanide(III) series but a direct comparison of the values can not be made due to the
different ionic strength and media. The first stability constants determined in this study
are within 2 standard deviations of the reported values except for the values determined
with La(III) at 0.5 M ionic strength. The second stability constants determined by this
work tend to be slightly higher than the values from the literature. The nitrate ionic
media of the literature study could compete with the ligand, lowering the value compared
75
to the value determined in a non-complexing ionic media. The stability constants of DPA
are lower than the values reported for the coordination analog NTA (Table 5.5). The
stability constants of DPA and NTA values tend to have a smaller difference as the ionic
radius of the lanthanide(III) ion decreases. The lower stability constant values of DPA
are a result of the piperidine ring structure which can undergo an inversion of the
coordination site due to interchange of boat confirmations similar to cyclohexane. This
geometric transition of the piperidine is referred to as ring flip as discussed in section 1.4.
The ring flip would invert the amine and cause a lengthening of the Ln-N bond, reducing
the stability of the complex.
5.2.3 CA
The previously reported stability constant of CA with lanthanum(III) (Table 5.6)
is significantly lower than the value reported in this study, (Tables 5.3 and 5.4). The very
low ionic strength and the lack of experimental details of the previous study make further
comparison difficult. For the reported set of values, the first and second stability constant
values of CA (log 1 ranging from 6.92 0.12 to 7.18 0.15 and log 2 14.24 0.13 to
14.97 0.07 across the lanthanide(III) series) are an order of magnitude lower than the
values for dipicolinic acid, listed in Table 5.5. The non-aromatic piperidine ring structure
of CA causes the amine to change the coordination site geometry as the nitrogen atom
orbitals alternate from planar sp2 character to nonplanar sp3 character, discussed in
section 1.4. The non-aromatic amine would not be expected to be planar and would
alternate being above and below the plane of the ring.
The non-aromatic amine
rearrangement would also affect the position of the carboxylic acid groups, decreasing
their planarity. The alternating nitrogen position should introduce a longer solution Ln-N
coordination distance, while the alternating position of the coordination groups should
displace additional water molecules around the inner hydration sphere of the
lanthanide(III) ion upon coordination and slightly decrease the affinity of the ligand for
the coordinated metal compared to dipicolinic acid66,101. This agrees with results from
the laser fluorescence of Eu(III) that indicate that the first complex of CA displaces more
water molecules from the Eu(III) inner hydration sphere than the dipicolinic acid
complex. CA also shows a decreased lanthanide(III) ion size dependency relative to the
76
variation of dipicolinic acid stability constants across the lanthanide series. The smaller
size dependency may be explained by the longer Ln-N coordination bond, the alternating
coordination group geometry and the slightly increased bite size of the CA coordination
site due to the non-aromatic resonance form. The decreased stability constants can also
be explained by a reorientation of the proton and coordination sites of the imino atom of
the non-aromatic CA molecule, called nitrogen inversion. The nitrogen inversion inverts
the tetrahedral orbital configuration of the imino atom and breaks the coordination bond
until inversion occurs again or the ligand reorients to allow the lanthanide(III) ion access
to the lone pair of electrons on the nitrogen atom. The nitrogen inversion would weaken
the Ln-N coordination bond and decrease the stability of the complex compared to
dipicolinic acid.
5.3 Calorimetry
5.3.1 Ligand Protonation
5.3.1.1 DPA
The values for the change in entropy and enthalpy for the first protonation of the
free ligand for DPA, IDA and NTA at 25.000 0.001C and 0.5 M sodium perchlorate
media are listed in Table 5.7. Comparison of IDA and NTA indicates that the change of
enthalpy of protonation decreases with increasing size of the molecule.
H NMR
experiments indicate that the DPA molecule adapts different confirmations as the pH is
varied as seen in the behavior of the peak corresponding to the protons in the para
position, discussed in section 4.6.3. The proton is localized on the amine but can also be
associated with one or more of the carboxy groups, either directly or through one or more
water molecules. The added proton would change the hydration sphere around the amine
site. This increase in the organization of the DPA molecule would result in a net increase
of entropy as water molecules are released. The decrease of the H observed in the
series IDA, NTA and DPA may be related to a decreased polarity of the amine site
caused by the presence of additional electron donating alkyl groups.
5.3.1.2 CA
The H and S values for the first protonation, listed in Table 5.7, of CA cannot
be directly compared to dipicolinic acid due to the different functionality associated with
77
the first protonation of the molecules. The aromatic amine of dipicolinic acid is much
more acidic than the phenol or the aliphatic amine of the CA tautomers as can be
observed in the pKa1 values of dipicolinic acid and CA, 4.51 and 10.75 0.04,
respectively. The first acid dissociation constant of CA is more similar to the aliphatic
amine of NTA or the phenol of hydroxybenzene than to that of dipicolinic acid (Table
5.1). The H and S of protonation values, -23.7 kJ mole-1 and 127.3 J mole-1 K-1, are
also more similar to the values reported for NTA or hydroxybenzene (Table 5.5). Both
the potentiometry and calorimetry studies indicate that the first acid protonation constant
corresponds to either the phenol or aliphatic structure of the CA tautomers.
5.3.2 Change of Enthalpy
5.3.2.1 PDA
The heat of complexation of PDA is below the limit of detection of the
calorimeter used in these experiments. The low heat of complexation is due to the weak
lanthanide(III)-PDA complex, observed in the inability to measure the stability constants
by potentiometry.
5.3.2.2 DPA
The first DPA complexes of Ho(III) or Nd(III) have an endothermic change of
enthalpy and a large, positive change in entropy (11.5 2.9 kJ mole-1 and 221 10 J
mole-1 K-1 for Ho(III) and 11.8 3.0 kJ mole-1 and 242 11 J mole-1 K-1 for Nd(III)),
indicating that the complex formation is an entropy driven process. The second DPA
complex with Ho(III) or Nd(III) forms with a small, endothermic H and a large, positive
S (0.6 3.1 kJ mole-1 and 109 10 J mole-1 K-1 for Ho(III) and 1.0 3.3 kJ mole-1 and
203 11 J mole-1 K-1 for Nd(III)). The complexes of NTA form with an exothermic H
except in the case of the Ho-NTA that has a slightly endothermic enthalpy (Table 5.6).
Previous work has shown a trend relating the residual enthalpy, H, of
aminopolycarboxylate complexation of Nd(III) ions and the sum of the pKa values of the
amine functional groups of the ligand, Figure 5.114. The H is a value corresponding to
the amine-lanthanide(III) interaction and is calculated from H. The values of H is the
calculated by:
H = H n 6.5 kJ mole-1
78
Eq. 5.1
complexation where n is the number of coordinating carboxylate groups and each

carboxylate coordination is assumed to have a similar enthalpy change as an acetate
coordination.
The H value increases as the amine or amines of an
aminopolycarboxylate have decreased acid character. The values of dipicolinic acid,

IDA and N,N-ethylenediaminediacetic acid (EDDA) show significantly deviations from
the H-pKa(N) trend. The dipicolinic acid deviation has been explained by a shorter
bond distance between the lanthanide(III) ion and the nitrogen atom due to the more polar
nature of the aromatic amine4.
The IDA and EDDA deviations are due to longer
lanthanide(III) amine bond distances4. The DPA molecule does not have an imino site
but can undergo a ring flip as discussed in section 5.2.2. The ring flip would cause the
coordination site to fluctuate as the carboxy groups convert between axial and equatorial
positions. Then ring flip could also induce a nitrogen inversion as the N-acetate group
reorients to coordinate to the lanthanide(III) ion. If the carboxylate coordinations of DPA
behave similarly to acetate coordination, then the lower H values of the Nd-DPA
complex suggests that the Nd-N bond distance of the DPA complex is longer than the
typical bond distance of the selected aminopolycarboxylate ligands.
The apparent
decreased Nd-N interaction of DPA can be related to the ring structure that restricts the
geometry of the coordination site. The aminopolycarboxylate ligands included in Figure
5.1 are straight chain aliphatic molecules except -picolinic acid, dipicolinic acid and
trans-1,2-diaminocyclohexanetetraacetic acid (DCTA). DCTA does not have a cyclic
structure involved in the molecular geometry of the acetate groups. Dipicolinc acid and
-picolinic acid also have ring structures directly attached to the carboxy groups but
cannot be directly compared to DPA due to the aromatic nature of both the ring structure
and the amine of these ligands. The carboxylic acid groups of DPA may have longer
coordination bonds and weaker interactions with the lanthanide(III) ions than acetate due
to restricted molecule geometry of the piperidine ring. If the carboxy coordinations are
weaker, the method used to calculate H would not represent the Ln-N interaction and
meaningful comparisons to other aminopolycarboxylate ligands cannot be made.
5.3.2.3 CA
79
The H values determined in this study for Ho(III) and Nd(III) complexation with
CA, 20.1 3.8 J mole-1 K-1 for Ho(III) and 14.7 3.8 J mole-1 K-1 for Nd(III), do not
agree with the literature values listed in Table 5.6. The values are difficult to compare
due to the different ionic strengths, 0.001 M versus 0.50 M. The change of enthalpy of
CA also does not agree with the values reported for dipicolinic acid even though a
tautomer of CA and dipicolinic acid have an identical coordination site. The dipicolinate
complex formation reactions are exothermic while the CA complex formation reactions
are endothermic. The H of CA would be expected to be lower than dipicolinic acid due
to the increased aliphatic nature of the amine which typically are less exothermic
complexes formation reactions with lanthanide(III) ions. The increased H of aromatic
amine coordination has been explained by a decreased distance between the
lanthanide(III) ion and the amine4 but there is not a significant difference in the Gd-N
distance reported in the crystal structures of CA102 and dipicolinic acid103. The average
Gd-O bond of dipiconlinic acid is slightly shorter than the Gd-O bond distance of CA,
2.395 6 versus 2.447 5, and is caused by increased interligand repulsion of the
[Gd(CA)3]3- species versus the [Gd(Hdipic)(dipic)]0 species.
The solid state bond
distances may not represent the aqueous lanthanide(III) coordination distances as the
complexes would be expected to fluctuate more in an aqueous environment. Assuming
the carboxylic acid coordinations of dipicolinic acid and CA are similar, the low H of
CA, Figure 5.1, must indicate an increased Ln-N bond distance. Unlike dipicolinic acid,
CA has both a phenolic aromatic and a keto-diene resonance form2,3. The imino group in
the non-aromatic keto form of CA can undergo nitrogen inversion and can cause
elongation of the Ln-N bond, discussed in section 5.2.3. The carboxylic acid groups of
CA and dipicolinic acid may not coordinate similarly. The hybridization of the amine
orbitals changes in these resonance forms from sp2 in the aromatic form to sp3 in the
diene form. The geometry of the N bonds would change from a planar confirmation
(sp2 = trigonal planar) to a non-planar confirmation (sp3 = tetrahedral) as discussed in
5.2.3. The tetrahedral imino alters the geometry of the carboxylic acid groups on the CA
molecule and could cause them to reorient out of the plane of the molecule and change
the interaction of the carboxy groups with the lanthanide(III) ion. The reoriented carboxy
80
coordinations may not be similar to acetate and so the H value would not represent a
Ln-N interaction.
5.3.3 Change of Entropy
5.3.3.1 PDA
The heat of complexation of PDA is below the limit of detection of the
calorimeter used in these experiments. The low heat of complexation is due to the weak
lanthanide(III)-PDA complex, observed in the inability to measure the stability constants
by potentiometry.
5.3.3.2 DPA
NTA and DPA have similar S values for the formation of the first Ho(III)
complexes while DPA has a larger change of entropy that NTA upon formation of the
first Nd(III) species (Table 4.6 and 5.5).
The S value of the first complex between
Nd(III) and a series of aminopolycarboxylate ligands has been shown to be related to the
number of inner sphere water molecules displaced during by complexation, Figure 5.214.
The value for DPA fits the general trend of increased S with increased number of
carboxylate
bonds
but
is
slightly
higher
than
other
tricarboxylic
acid
aminopolycarboxylate ligands. The slightly larger S values of the first complex of DPA
versus NTA indicates that DPA displaces a larger number of water molecule than NTA
upon coordination to Nd(III). This agrees with results from fluorescence experiments
that noted increased water displacement from the Eu(III) inner hydration sphere upon
coordination of DPA compared to NTA.
The additional water molecules are displaced by fluctuations of the coordination
site caused by the piperidine ring flip.
The ring flip causes reorientation of the
carboxylate and amine coordinations.

The S value of the second complex formation of DPA and NTA agree well for
Ho(III). The second complex of Nd-DPA has a significantly higher S value than the
corresponding NTA complex, indicating that additional water molecules are displaced
from the Nd(III) inner hydration sphere upon DPA complex formation. The increased
dehydration of Nd(III) during the second complex formation is caused by the piperidine
ring flip as discussed for the first complex formation. The significant difference between
81
the values of Nd(III) and Ho(III) are probably related the inter-ligand charge repulsion
which would be greater for the smaller Ho(III) ion. The repulsion would increase the HoDPA coordination distances and so displace fewer inner sphere water molecules than the
Nd(III) ion complex.
5.3.3.3 CA
The La-CA S value, Table 4.7, does not agree with the value previously reported
(Table 5.6), but comparison is difficult due to the different ionic strengths. The S
values of complex formation are larger for CA than those of dipicolinic acid but follow
the same trend of increased entropy as the lanthanide(III) radii decrease30. The S value
for the Nd-CA complex formation is higher than typical dicarboxylic acid
aminpolycarboxylate ligands, shown in Figure 5.2. This indicates that CA displaces an
additional water upon complex formation when compared to dipicolinic acid.
This
agrees with results from laser fluorescence which indicate that CA displaces additional
water molecules from the Eu(III) inner coordination sphere compared to the number
discplaced by complexation by dipicolinic acid. The additional waters are displaced from
the inner hydration sphere of the lanthanide(III) ions because CA has varying carboxy
and amine coordination geometry due to the keto tautomer and possible nitrogen
inversion, discussed in section 5.2.3.
The formation of the second complexes of Nd(III) and Ho(III) have S values
similar to the formation of the first complex and are much higher than the values
observed with dipicolinic acid, Table 5.8. The fluorescence results indicate that a similar
number of water molecules are displaced from the Eu(III) inner hydration sphere by the
second complexation of both the CA and dipicolinic acid, discussed in section 5.5. The
higher S values for the second CA complex formation can be explained by additional
reorganization caused by the phenol-keto functional group.
Upon coordination, the
deprotonated phenol would reorganize water molecules in the secondary lanthanide(III)

hydration sphere as well as the primary phenol hydration sphere to stabilize the charge of
the functional group. These additional displaced water molecules can contribute to both
the first and second S values for CA coordination.
82
5.4.1 PDA
The change in the oscillator strength caused by complexation of PDA was too
weak to allow the determination of a PML value.
5.4.2 DPA
The values of the oscillator strengths determined in this study are listed in Table
4.10. Previously measured oscillator strengths of IDA, NTA, dipicolinic acid and CA are
listed in Table 5.9. The oscillator strength of the Nd(III) and Ho(III) aquo ions are
considered to have values of 9.68 x 10-6 and 6.12 x 10-6, respectively53. The oscillator
strengths of the aquo ions determined in this study are within 2 or 3 standard deviations
of these values.
The oscillator strength values determined for the first complexes of DPA are
within 1 standard deviation of the values reported for the first complex of NTA,
molecules with a similar coordination site. The PML2 of DPA are higher than those
reported for NTA and are similar to the value seen for IDA. The reported oscillator
strength values of NTA show similar values for the first and second complex, indicating
that the formation of the ML2 species significantly decreases the amount of covalent
interaction between the ligands and the lanthanide(III) ion.
The plots of P versus [L] : [M], Figures 4.1 and 4.2, have 3 distinct regions. The
oscillator strength increases linearly with the concentration of the species, showing the
formation of ML and ML2 complexes. After the ML2 species forms, the oscillator
strength becomes constant, indicating that either any ML3 species does not form in
significant concentrations or that the covalancy term of the ML3 does not affect the
hypersensitive transition as is observed with NTA53. Since an ML3 complex is not
expected to form with the tetradentate DPA ligand, the lack of this species seem
reasonable and confirms the coordination model used in stability constant determination.
5.4.3 CA
The PML values of CA determined in this work do not agree with the values found
in the literature. The oscillator strength values of dipicolinic acid and IDA are much
higher in the Devlin et al. and Stephens et al. studies compared to the values reported by
Fellows et al. as listed in Table 5.9. It is not readily apparent why the dipicolinic acid
83
and IDA values of these studies have such large differences since similar values were
determined for the aquo ions. Since the Devlin et al. and Stephens et al. studies were
performed by the same scientific group but reported significantly different oscillator
strength values for IDA and dipicolinic acid, use of these values for comparison seems
unreliable. Most of the CA oscillator strengths agreed, within 1 standard deviation, with
the values reported Fellows et al. for dipicolinic acid, a molecule with a similar
coordination sites as CA. The value determined for Ho-CA was lower than the value
reported for Ho-dipicolinic acid, 12.15 0.21 versus 14.26. The value of the Hodipicolinic acid from Fellows et al. appears to be higher than would be expected as
oscillator strengths of Nd(III) are higher than those of Ho(III) for oscillator strength
values below 20 and may reflect an increased hypersensitivity between Ho(III) and
dipicolinic acid52,53.
The plots of P versus [L] : [M], Figures 4.1 and 4.2, have different profiles for
Nd(III) and Ho(III). Figure 4.1 shows 3 regions with positive slope, indicating the
formation of 3 different complexes with Nd(III) which are most probably ML, ML2 and
ML3 species. Figure 4.2 has 2 regions with positive slope and one region of constant
values, indicating that Ho(III) forms two complexes with CA and the third species either
forms in low concentrations or that the covalancy term of that species does not affect the
hypersensitive transition as discussed with DPA in section 5.4.1. The different ML3
profiles indicates that the size of the lanthanide(III) ion may prevent formation of the
third CA complex due to increased steric crowding and inter-ligand charge repulsion.
5.5 Eu(III) Laser Fluorescence
5.5.1 PDA
The Eu(III) fluorescence peaks, coordination number of the ligand and the
number of water molecules in the inner hydration sphere of the Eu(III) ion for the various
species of this study and other ligands of interest are listed in Table 5.10. The number of
water molecules was calculated assuming that the inner coordination sphere of the aquo
Eu(III) ion is occupied by 9 water molecules89,104. A single peak was observed at 17273
cm-1 for PDA complexation throughout all studies including varying pH from 2 to 6 and
from ligand to metal concentration ratios of 0.1 to 5. The peak position of the PDA
84
species is the same as the value reported for the first acetate complexation (Table 5.8).
This indicates that PDA is forming only a weak complex through a single carboxylic acid
which displaces a single water from the inner coordination sphere of the Eu(III) ion. The
number of water molecules in the inner hydration sphere of the Eu(III) ion could not be
determined because the PDA peak was too weak under all conditions.
5.5.2 DPA
The Eu(III) fluorescence spectra of the previously reported NTA complex was
performed on solid material and so comparisons to solution systems have to be made with
the consideration that the aqueous system has a less rigid coordination system in which
the coordinated ligands can still rapidly exchange. The ML species of DPA exists in two
different environments (Table 5.10). The first Eu-DPA environment has a similar peak
position as NTA (Table 5.10). The number of water molecules in the inner hydration
sphere of Eu(III) of DPA is slightly lower than the value reported for NTA and the ligand
coordination number of DPA is slightly higher than the value reported for NTA. The
difference in number of water molecules and ligand coordination number indicates that
the DPA complex occupies a larger area in the inner coordination sphere of Eu(III) than
the NTA complex due the piperidine ring flip. The ring flip would cause the carboxy and
amine coordination groups to reorganize around the metal ion.
This reorientation
corresponds to the hump that was always observed on the peak of the first complex that
represents the conversion from one ring form to another.
5.5.3 CA
The peak positions of the CA complexes with Eu(III), listed in Table 4.11, agree
the values reported previously within 1 or 2 cm-1 (Table 5.8). The calculated ligand
coordination number is within 1 standard deviation of the values reported in the literature.
The peak positions values of dipicolinic acid from previous studies generally vary within
1 or 2 cm-1. The ligand coordination numbers are similar to the values reported for CA.
The first dipicolinic acid complex has a Eu(III) hydration number of 3.2, indicating that
only 3 waters are displaced. The number of water molecules in the inner sphere of the
Eu(III) ion are slightly lower than those predicted in the literature which assumed the
tridentate CA molecule would displace 3 water molecules. The CA molecule displaced 4
85
to 5 water molecules upon forming the first complex due to the keto tautomer. As the
molecule switches between the keto and phenol tautomers, the coordination sites would
change geometric positions and additional water molecules are displaced. The second
CA complex has an average of 3 water molecules displaced per ligand. The decrease in
the number of displaced water molecules indicates that the CA molecules of the second
complex have a slightly longer coordination bonds due to inter-ligand charge repulsion,
causing each ligand to occupy a smaller area in the inner coordination sphere of the
Eu(III) ion.
5.6 NMR
5.6.1 PDA
The 1H NMR of Eu-PDA system was performed at varying pH and did not exhibit
the shift in the peaks expected upon the complexation of the paramagnetic Eu(III) ion.
Previous work has studied the lanthanide(III) complexes of dipicolinic acid105 and CA106
by NMR and PMR. Diamagnetic lanthanide(III) ion shift the position of the 1H NMR
peaks of the complexed ligands107. This shift was not observed in the Eu-PDA system.
Additionally, the PDA peaks did not show significant 1H NMR peak broadening that
would have been expected if the paramagnetic Eu(III) complexed the ligand17. This
indicates that the Eu-PDA complex was only a minor species that was not detected by the
NMR measurement.
5.6.2 DPA
The 1H NMR spectra of La(III) and Lu(III) DPA complexes have very different
(Appendix C). The La(III)-DPA spectrum has very broad peaks while the 1:1 and 1:2
Lu(III)-DPA spectra have sharp peaks that retain their multiplicity. The spectra of DPA
and the 1:1 [Lu(III)]:[DPA] system had the same number of peaks but all peaks had
different chemical shifts. The sharpness of the peaks indicates that Lu-DPA kinetics
were faster than the NMR time scale. The broadness observed in the peaks of the 1:1
[La(III)]:[DPA] spectrum indicates that this complex is undergoing an equilibrium on the
NMR time scale with the broad peaks representing the average of two or more systems.
This suggests that DPA complex formation is sensitive to changes in the size of the
lanthanide ion with larger lanthanide(III) ions having slower reaction rates. The 1:1
86
[La]:[DPA] system was studied temperatures as low as 5.0C but the peaks remained
coalesced. The equilibrium may be the DPA piperidine ring flip with the broad peaks
representing the transition from one chair form of DPA to the other chair form, involving
boat and twist boat configurations of the ring.
The 1H NMR peaks of 1:2 [Lu]:[DPA] systems are sharp and retain their
multiplicity but have peaks that are also in the 1:1 [Lu]:[DPA] systems as well as
additional peaks. The similar peaks in the 1:1 and 1:2 [Lu]:[DPA] system indicates that
one of the DPA ligands in the ML2 complex is similar to the DPA in the ML species
while the additional peaks in the 1:2 [Lu]:[DPA] system indicates that the second DPA
ligand in the ML2 species must be in a different coordination environment. The steric
bulk and inter-ligand charge repulsion of the second complexed DPA must cause this
molecule to have a different orientation around the metal ion.
5.6.3 CA
13
C NMR experiments were performed on CA as well as on the Ca complexes of
La(III) and Lu(III). The 13C NMR peaks of the carbon shifted slightly. The alkene and
aromatic carbon peaks are located at similar chemical shift and any effects on the
tautomer specition of CA could not be discerned using this technique.
5.7 Crystallography
The crystal structure of CA has been previously determined70. The molecule was
observed as a monohydrate zwitterion with a protonated amine and a deprotonated
carboxylic acid. The other carboxylic acid and the phenol were also protonated. The
crystal structure of the Gd-CA complex102 has also been determined and shown to exist as
a Na5Gd(CA)2(HCA) complex with 16 waters of hydration. Two CA molecules are
completely deprotonated while one complex has a phenolic hydrogen. The authors fail to
mention how the hydrogen atom position was assigned and also state that the water
molecules were disordered. The phenolic proton could be reassigned as a proton of a
water molecule that was hydrogen bonded to the CA, linking the Eu(CA)3 units.
Several studies report coordination distances for metal ion and the amine and
carboxy oxygen atoms for CA18,108 and dipicolinic acid20,109,110.
The coordination
distances of Fe(III)OH(L), when L = CA or dipicolinic acid, have values that agree

87
within 2 standard deviations20. The coordination distance of [Gd(HxL)3]-n species, where

L = CA or dipicolinic acid, are slightly longer for the CA18 system than the values
calculated for dipicolinic acid18. The Gd(III) coordination distances reported in [18] were
calculated from data reported in [19]. Although errors are not reported for the dipicolinic
acid values, the coordination distances probably agree within 2 standard deviation values.
The bond lengths reported for [Ho(Hdpic)(dipic)] species21 agree with the bond lengths
reported for the [Gd(dipic)3]2- species19 within 0.5%. The CA ring structure is more
strained than the dipicolinate ring, observed by a ~3% lengthening of the bonds to the
carbon in the para position relative to the amine.
The crystal structures determined for PDA exhibited ~30% zwitterion behavior,
calculated from the relative proton density as calculated by least square refinement where
one carboxylic acid was founded to only account for ~70% of a proton. The DPA
molecule was founded exclusively as the zwitterion with full deprotonation of a
carboxylic acid group.
5.8 Conclusions
5.8.1 PDA
The acid dissociation constants determined by this work indicate that PDA is
triprotic instead of a diprotic acid as reported in the literature63,64. The results from this
work strongly disagree with the results reported by Thompson64 for the lanthanide(III)
stability constants of PDA. The PDA of this study was identified as the cis form of the
compound by diffractometry. The ligand of the previous study might be suspect as it was
not synthesized by the author and was characterized using elemental analysis.
All
techniques used in this work reported weak, monodentate complexation of lanthanide(III)

ions by PDA. The coordination structural analog, IDA, has first stability constants of
ranging between 105.31 to 106.71 for the lanthanide(III) series.
The dissimilarity in
complex strength of IDA and PDA can be explained by the PDA piperidine ring flip that
reorients the coordination site, preventing chelate formation. The imino atom of the PDA
molecule would also have a nitrogen inversion during the ring flip that would destabilize
and lengthen any Ln-N coordination bonds.
5.8.2 DPA
88
The acid dissociation constants and lanthanide(III) stability constants show good
agreement with the values previously reported for DPA. The DPA stability constants
increase as the size of the lanthanide(III) radii decrease for both the first and second
complexes. The complex formation is entropy driven and displaces 5 and 8 water
molecules as DPA coordinates in tetradentate fashion to form first and second complexes,
respectively. The larger number of water molecules displaced by the first complex and
the decreased lanthanide(III) complex stability can be explained by the DPA piperidine
ring flip which would reorient the coordination groups, causing the coordination groups
to displace additional water molecules from the inner coordination sphere of the metal
ion. Larger lanthanide(III) ions appear to have slower ring reorientation as observed in
1
H NMR experiments, indicating that smaller lanthanide(III) ions are a better fit for the
coordination site of DPA. The endothermic H values also indicate that the average
coordination distances may be longer than in straight chain aminopolycarboxylate
ligands. The longer coordination distances would be caused by the coordination site
reorientation caused by the piperidine ring flip. This ring flip reorientation kinetics may
explain the improved the lanthanide(III) size selectivity of DPA compared to a straight
chain molecule NTA.
5.8.3 CA
The acid dissociation constants show general agreement with those found in the
literature. The CA stability constants are slightly lower and have less change across the
lanthanide(III) series compared to dipicolinic acid. The formation of the first complex is
entropy driven and displaces 4 to 5 water molecules from the inner hydration sphere. The
additional water molecules displaced during the complexation of the first ligand can be
explained by the keto tautomer that removes the planar geometry of both the amine and
the carboxy groups. The formation of the second complex is entropy driven and each
ligand displaces 3 water molecules from the inner hydration sphere. The size of the
lanthanide(III) ion is important in the formation of the ML3 species. The hypersensitive
spectrum of Nd clearly indicates the formation of a ML3 complex while this species is not
observed for the Ho(III) system (Figure 4.1 and 4.2). The tautomer forms of CA appear
89
to create a larger, fluctuating coordination site that reduces the lanthanide(III) size
selectivity compared to dipicolinic acid.
5.8.4 Steric Hindrance of Aminopolycarboylic Ligands
5.8.4.1 Piperidine Ring
Aminopolycarboxylate ligands with carboxy groups directly attached to the
piperidine ring appear to decrease the complexation stability.
The ring flip of the
piperidine ring can reorient the coordination groups. In the case of PDA, the ring flip
dominates the lanthanide(III) coordination chemistry and reduces the ligand to the
formation of very weak complexes similar to those observed with acetate. DPA forms
stable complexes but displaces additional water molecules upon formation of the first
complex compared to the coordination structure analog NTA. The additional displaced
water molecules can be observed both by the decreased Eu(III) waters of hydration of the
complex measured by fluorescence and the increased change of entropy of complex
formation measured by calorimetry.
DPA does not follow the trend of increasing
H(N) with increasing pKa(N) that has been noted for straight chain aliphatic
aminopolycarboxylate ligands. The deviation from of H(N) is most likely related to
the piperidine ring flip that would weaken the carboxylate coordinations and the Ln-N
coordination by increased coordination bond lengths, as observed in the change of
enthalpy determined by calorimetry. NMR experiments indicate that the piperidine ring
flip appears to be less significant for smaller lanthanide ions like Lu(III) and may be the
cause of the increased size selectivity of DPA compared to NTA.
5.8.4.2 CA
The tautomerization of CA causes the lanthanide(III) complexes to be less stable
than with dipicolinic acid. The non-aromatic tautomer introduces non-planar alignment
of both the amine and the carboxylic acid groups. The fluctuation of the coordination
sites causes additional water molecules to be displaced from the inner hydration sphere as
observed in both number of waters in the inner coordination sphere of Eu(III) as
determined by flourescence and the change of entropy determined by calorimetry. The
fluctuation of the coordination groups increases the lanthanide(III) coordination bond
lengths as seen in the change of enthalpy determined by calorimetry. The size of the
90
lanthanide(III) ions appears to have more influence on the formation of ML3 complex
with CA than with dipicolinic acid due to the increased steric crowding caused by
fluctuation of the coordinating groups of the CA molecule.
5.9 Future Work
The coordination bond lengths of PDA, DPA and CA appear to be longer due to
effects caused by the ring structures. CA appears to have different coordination geometry
in solution than in solid state. Experiments using EXAFS techniques could measure the
coordination bond lengths and examine the CA geometry to confirm any differences from
the values of the solid state materials. Synthesis of a methoxy form of chelidamic acid
may eliminate the tautomerization and the resulting compounds should behave more
similarly to dipicolinic acid. Although 5.0 C NMR experiments were not able to resolve
the coalesced La-DPA peaks, low temperature studies might give insight into the kinetics
of the ring flip and the influence of the ring flip on the coordination chemistry of DPA
and PDA. Ring structures could be incorporated into future ligand design if the enhanced
size lanthanide(III) selectivity of DPA over NTA is related to the kinetics of the DPA
piperidine ring flip. Additional studies of the lanthanide(III) coordination chemistry with
ligands such as piperidine-2-carboxylic acid and 2-carboxypiperidine-N-acetic acid may
establish
trends
in
the
thermodynamic
aminopolycarboxylic ligands
91
values
for
structurally
hindered
Table 5.1.
Acid dissociation constant values for PDA, DPA and CA at 0.1 M I.
ligand
PDA
DPA
CA
log Ka1
log Ka2
9.92
log Ka3
ionic media
T (C)
ref
2.87
0.1 M KCl
30
63*
10.12
2.54
0.1 M KNO3
25
64*
9.33
2.71
1.3
0.1 M KNO3
25
73*
10.88
3.11
1.4
0.1 M NaNO3
20
67*
10.85
3.18
1.9
0.1 M NaClO4
22
68*
11.4
3.47
<2
0.05 to 0.1 M
25
66*
10.8
3.2
0.1 M NaClO4
25
66**
* Determined by potentiometric titration.

** Determined by spectrophotometric titration.
92
Table 5.2.
Acid dissociation constant values for IDA, NTA, dipicolinic acid and hydroxybenzene.
ligand
IDA
NTA
dipicolinic acid
hydroxybenzene
log Ka1
log Ka2
log Ka3
ionic media
9.34
2.62
1.77
0.1 M
9.20
2.57
1.8
0.5 M
9.68
2.79
9.46
2.52
1.81
0.1 M
8.94
2.31
1.78
0.5 M
9.08
2.46
1.78
2.0 M NaClO4
4.66
2.07
0.1 M
4.51
2.05
0.5 M
T (C)
ref
25
85*
25
85*
25
85*
25
85*
2.0 M NaClO4
9.77
0.1 M
93
Table 5.3.
The lanthanide(III) stability constants of PDA and DPA*, T = 25 C, I = 0.1 M KNO3.
PDA64
DPA111
Ln(III)
log 1
log 2
log 1
log 2
La
5.31
9.37
9.17
15.34
Nd
5.92
10.80
10.18
17.50
Eu
6.13
11.45
10.63
18.54
Ho
6.32
11.87
11.18
19.35
Lu
6.71
12.55
11.74
20.66
94
Table 5.4.
Lanthanide(III) stability complexes with IDA85, NTA85 and dipicolinic acid85*, T = 25 C,
I = 0.1 M KNO3.
NTA
IDA
Ln(III)
log 1
log 2
La
5.88
Nd
log 3***
dipicolinic acid**
log 1
log 2
log 1
log 2
log 3
9.97
10.47
17.84
7.94
13.71
17.95
6.50
11.39
11.10
19.51
8.73
15.40
20.41
Eu
6.73
12.11
15.79
11.32
20.64
8.79
15.86
21.32
Ho
6.97
12.47
16.28
11.76
21.06
8.69
16.15
21.91
Lu
7.61
13.73
16.15
12.32
21.65
9.00
16.72
21.32

** Determined in 0.5 M ionic strength.
*** Determined in 1.0 M NaClO4.
95
Table 5.5.
Previously determined thermodynamic values* of CA with the lanthanum(III) ion112, T =
25C, I = 0.001 M NaClO4.
log 1
H1 (kJ mole-1)
S1 (J mole-1 K-1)
6.58
-9.4
95
* Determined by spectrophotometric titration.

112. Y. Ducommun, L. Helm, G. Laurenczy and A. E. Merbach, Inorg. Chim. Acta.
1989,158, 3.
96
Table 5.6.
Thermodynamic values for the first protonation of the IDA85, NTA85, dipicolinic acid85,
4-hydroxypyridine and hydroxybezene85, T = 25C, I = 0.5 M NaClO4.
ligand
H (kJ mole-1)
S (J mole-1 K-1)
IDA
-34
61.5
NTA
-22
102
dipicolinic acid
0.8
89.1
4-hydroxypyridine
-6.23*
41*
hydroxybenzene
-24.6
104**
* Determined for 0 M ionic strength.

** Determined at 0.1 M ionic strength.
97
Table 5.7.
Thermodynamic values of lanthanide(III) complexation with IDA, NTA and dipicolinic
acid, T = 25C, I = 0.5 M85.
ligand
IDA
Ln(III)
Ho
Ho
NTA
Nd
Ho
dipicolinic acid
Nd
Hn (kJ mole-1 )
Sn (J mole-1 K-1)
1*
133*
-7.2*
75*
0.8
225
-21**
106**
-6.2
184
-16**
108**
-8.3
138
-16.7
84
-16
110
-17
71
* Determined at 1.0 M ionic strength.

** Determined at 0.1 M ionic strength.
98
80
DTPA
70
-H
-1
(kJ mole )
60
EDTA
50
HEDTA
40
30
dipic
NTA
20
10
EDDA
IDA
DPA
0
L-p
-10
0
CA
12
16
20
pKa(N)
24
28
32
36
Figure 5.1.
The relationship between the residual enthalpy, H, of the first complex formation with
Nd(III) and the total basicity of the nitrogen donor atoms of select polycarboxylate
ligands*.
* -picolinic acid (p)14; dipicolinic acid (dipic)85; L-proline(L-p)113; iminodiacetic acid
(IDA)85; nitrilotriacetic acid (NTA)14; N, N-ethylenediaminediacetic acid (EDDA)14; Nhydroxyethylenediaminetriacetic acid (HEDTA)14; ethylenediaminetetraacetic acid
(EDTA)14; Diethylenetriaminepentaacetic acid (DTPA)14.
99
400
350
-1
-1
S1 (J mole K )
300
DPA
250
TMEDTA
BMA EDTA
MEDTA
EDPDA
CA
NTA
HEDTA
EDDA
dipic
L-p
IDA
ac
200
150
100
50
DTPA
0
0
number of carboxy groups
Figure 5.2.
Correlation of S1 of Nd(III) and the number of carboxylate groups with acetate (ac) and
select polycarboxylate ligands*.
* -picolinic acid (p)14; L-proline (L-p)11; iminodiacetic acid (IDA)85; dipicolinic acid
(dipic)85; N, N-ethylenediaminediacetic acid (EDDA)14; Nhydroxyethylenediaminetriacetic acid (HEDTA)14; nitrilotriacetic acid (NTA)14; Nmethyethylenediaminetriacetic acid (MEDTA)14; diethylenetriaminopentaacetic acid
bis(methylamide) (BMA)14; ethylenediamine-N,N-dipropionic-N,N-diacetic acid
(EDPDA)14; ethylenediaminetetraacetic acid (EDTA)14; 1,4tetramethylenediaminetetraacetic acid (TMEDTA)14; Diethylenetriaminepentaacetic acid
(DTPA)14.
100
Table 5.8.
Nd(III) and Ho(III) oscillator strength values for NTA, IDA, dipicolinic acid and CA*.
Ln(III)
ligand
PM / 106
PML / 106
PML2 / 106
ref
NTA
9.77
13.03
13.01
53
9.71
12.89
16.93
53
9.08
15.28
114
8.65
18.0
115
9.51
14.41
9.08
18.15
114
8.65
19.2
115
9.08
26.25
114
6.11
11.09
11.73
53
6.20
11.32
11.67
116
6.13
10.34
14.94
53
5.91
18.45
115
5.98
14.26
53
5.91
22.80
115
5.91
33.88
115
IDA
Nd
dipicolinic acid
CA
NTA
Ho
IDA
dipicolinic acid
CA
* Species are indicated by the subscript of P.
101
22.49
53
Table 5.9.
Eu(III) fluorescence peaks for acetic acid, dipicolinic acid, CA, NTA and IDA ligand
species*.
ligand
peak (cm-1)
[117]
[91]
17272
17275
17276
[Eu(H2O)9]3+
17273
[Eu(ac)(H2O)x]2+
17271
[Eu(ac)2(H2O)x]1+
17265
[Eu(ac)3(H2O)x]0
acetic acid
17267
17268
17267
[Eu(IDA)(H2O)6]1+
17252
17254
17250
[Eu(IDA)2(H2O)3,4]1-
17235
17238
17233
[Eu(IDA)2]3-
17263
17264
17265
[Eu(dipic)(H2O)6]1+
17248
17249
17251
[Eu(dipic)2(H2O)3]1-
17231
17232
17234
[Eu(dipic)3]3-
IDA
dipicolinic
acid
CA
[118]
species
[61]
17265
[Eu(CA)(H2O)x]1+
17251
[Eu(CA)2(H2O)x]1-
17235
[Eu(CA)(H2O)x]3-
17263**
NTA
17261
[Eu(NTA)(H2O)4,5]0
17251
[Eu(NTA)( H2O)x]0
17241
[Eu(NTA)2 H2O)x]3-
* Bracket indicates the reference number from which the data was taken. Subscript x
denotes the number of water molecules has not been directly determined.
** Value was measured in solid state sample.
102
Table 5.10.
Eu(III) waters of hydration and ligand coordination numbers for acetic acid, dipicolinic
acid, CA, NTA and IDA ligand speciesa.
ligand
nH2O
CNL
species
9.6[117], 9.0[89]
0.6[91]
[Eu(H2O)9]3+
1.4[91]
[Eu(ac)(H2O)x]2+
1.9[91]
[Eu(ac)2(H2O)x]1+
3.2[91]
[Eu(ac)3(H2O)x]0
6.3[119]
2.6[91]
[Eu(IDA)(H2O)6]1+
3.6[119]
5.7[91]
[Eu(IDA)2(H2O)3,4]1-
2.1[119]
9.2[91]
[Eu(IDA)2]3-
6.3[117]
3.2[91]
[Eu(dipic)(H2O)6]1+
3.1[117]
6.4[91]
[Eu(dipic)2(H2O)3]1-
0.3[117]
10.1[91]
[Eu(dipic)3]3-
3.2[91]
[Eu(CA)(H2O)x]1+
6.6[91]
[Eu(CA)2(H2O)x]1-
10.3[91]
[Eu(CA)x]3-
3.7[91]
[Eu(NTA)(H2O)4,5]0
acetate
IDA
dipicolinic
acid
CA
NTA
4.5[120]
a. Bracket indicates the reference number from which the data was taken. Subscript x
denotes the number of water molecules has not been directly determined.
b. The value of n = 1 or 2 between pH 2 and 6.
103
APPENDIX A.
Hypersensitive Spectroscopy
104
0.35
0.30
Absorbance
0.25
0.20
0.15
0.10
0.05
0.00
16600
16800
17000
17200
17400
17600
17800
18000
-1
wave number (cm )
Figure A.1.
The spectrum of 4.93 mM Nd(III), I = 2.00 M NaClO4, pH = 2.80 and T = 23C.
105
0.16
0.14
0.12
Absorbance
0.10
0.08
0.06
0.04
0.02
0.00
-0.02
21000 21250 21500 21750 22000 22250 22500 22750 23000 23250 23500
wave number (cm-1)
Figure A.2.
The spectrum of 4.04 mM Ho(III), I = 2.00 M NaClO4, pH = 2.93 and T = 23C.
106
0.4
Absorbance
0.3
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
0.2
0.1
0.0
16600
16800
17000
17200
17400
17600
17800
18000
wave number (cm-1)
Figure A.3.
The hypersensitive transition spectra of 4.93 mM Nd(III) with varying [PDA], I = 2.00 M
NaClO4, pH = 5.48 to 5.81 and T = 23C. The concentration of PDA and the oscillator
strength of each spectrum are listed in Table A.1.
107
Table A.1.
The concentration of PDA and oscillator strength of spectra in Figure A.3.
Sample
[PDA], M
[L]:[M]
P(x106)
0.0000
0.000
8.89
7.80E-04
0.237
9.30
1.755E-03
0.435
9.41
3.899E-03
0.791
9.47
108
0.20
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Absorbance
0.15
0.10
0.05
0.00
21300
21600
21900
22200
22500
22800
23100
23400
wave number (cm-1)
Figure A.4.
The hypersensitive transition spectra of 4.04 mM Ho(III) with varying [PDA], I = 2.00 M
NaClO4, pH = 5.48 to 5.81 and T = 23C. The concentration of PDA and the oscillator
109
Table A.2.
The concentration of PDA and oscillator strength of spectra in Figure A.4.
Sample
[PDA], M
[L]:[M]
P(x106)
0.0000
0.000
6.01
2.859E-03
0.710
6.50
4.084E-03
1.01
6.56
5.309E-03
1.31
6.64
8.168E-03
2.02
7.17
110
0.35
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
0.30
Absorbance
0.25
0.20
0.15
0.10
0.05
0.00
16600
16800
17000
17200
17400
17600
17800
18000
wave number (cm-1)
Figure A.5.
The hypersensitive transition spectra of 4.93 mM Nd(III) with varying [DPA], I = 2.00 M
NaClO4, pH = 5.12 to 5.77 and T = 23C. The concentration of DPA and the oscillator
111
Table A.3.
The concentration of DPA and oscillator strength of spectra in Figure A.5.
Sample
[DPA], M
[L]:[M]
P(x106)
0.000
0.000
9.46
1.196E-03
0.243
10.12
2.790E-03
0.566
11.37
3.986E-03
0.809
11.79
5.182E-03
1.05
12.86
6.776E-03
1.37
13.29
7.972E-03
1.62
13.36
112
0.20
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Absorbance
0.15
0.10
0.05
0.00
21300 21600 21900 22200 22500 22800 23100 23400
wave number (cm-1)
Figure A.6.
The hypersensitive transition spectra of 4.04 mM Ho(III) with varying [DPA], I = 2.00 M
NaClO4, pH = 5.30 to 5.99 and T = 23C. The concentration of DPA and the oscillator
113
Table A.4.
The concentration of DPA and oscillator strength of spectra in Figure A.6.
Sample
[DPA, M]
[L]:[M]
P(x106)
0.0000
0.000
6.36
5.79E-04
0.143
6.99
1.351E-03
0.335
7.82
1.931E-03
0.478
8.49
2.510E-03
0.621
9.28
3.282E-03
0.812
10.17
3.861E-03
0.956
10.85
4.537E-03
1.12
11.61
114
0.60
0.55
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
0.50
0.45
Absorbance
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00
16600
16800
17000
17200
17400
17600
17800
18000
wave number (cm-1)
Figure A.7.
The hypersensitive transition spectra of 4.93 mM Nd(III) with varying [CA], I = 2.00 M
NaClO4, pH = 5.05 to 5.18 and T = 23C. The concentration of CA and the oscillator
115
Table A.5.
The concentration of CA and oscillator strength of spectra in Figure A.7.
Sample
[CA], M
[L]:[M]
P(x106)
0.000
0.000
9.42
1.722E-03
0.349
10.96
4.018E-03
0.815
13.20
5.740E-03
1.16
14.95
7.461E-03
1.51
16.16
9.757E-03
1.98
18.21
1.148E-02
2.33
19.30
1.406E-02
2.85
20.24
116
0.40
0.35
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Absorbance
0.30
0.25
0.20
0.15
0.10
0.05
0.00
21300
21600
21900
22200
22500
22800
23100
23400
wave number (cm-1)
Figure A.8.
The hypersensitive transition spectra of 4.04 mM Ho(III) with varying [CA], I = 2.00 M
NaClO4, pH = 5.05 to 5.18 and T = 23C. The concentration of CA and the oscillator
117
Table A.6.
The concentration of CA and oscillator strength of spectra in Figure A.8.
Sample
[CA], M
[L]:[M]
P(x106)
0.000
0.000
5.88
8.62E-04
0.213
7.66
2.010E-03
0.498
9.69
2.872E-03
0.711
11.50
3.733E-03
0.924
13.38
4.882E-03
1.21
15.77
5.744E-03
1.42
17.63
6.749E-03
1.67
19.76
118
Spectrum 1
Spectrum 2
Spectrum 3
Absorbance
0.15
0.10
0.05
0.00
21500
22000
22500
23000
23500
-1
wave number (cm )
Figure A.9.
The hypersensitive transition spectra of 4.04 mM Ho(III) and 1.66 mM DPA with
varying pH, I = 2.00 M NaClO4 and T = 23C. The pH and the oscillator strength of each
spectrum are listed in Table A.7.
119
Table A.7.
The pH and oscillator strength of spectra in Figure A.9.
Sample
[L]:[M]
pH
P(x106)
0.411
2.38
6.05
0.411
3.18
8.36
0.411
5.05
9.18
120
0.25
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Absorbance
0.20
0.15
0.10
0.05
0.00
21300
21600
21900
22200
22500
22800
23100
23400
-1
wave number (cm )
Figure A.10.
The hypersensitive transition spectra of 4.04 mM Ho(III) and 6.29 mM DPA with
varying pH, I = 2.00 M NaClO4 and T = 23C. The pH and the oscillator strength of each
121
Table A.8.
Sample
[L]:[M]
pH
P(x106)
1.56
2.08
10.48
1.56
3.25
12.13
1.56
4.40
13.11
1.56
5.21
13.99
122
0.45
0.40
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
0.35
Absorbance
0.30
0.25
0.20
0.15
0.10
0.05
0.00
16600
16800
17000
17200
17400
17600
17800
18000
wave number (cm-1)
Figure A.11.
The hypersensitive transition spectra of 4.93 mM Nd(III) and 4.78 mM CA with varying
pH, I = 2.00 M NaClO4 and T = 23C. The pH and the oscillator strength of each
123
Table A.9.
Sample
[L]:[M]
pH
P(x106)
0.968
2.34
14.08
0.968
3.27
14.06
0.968
3.66
13.98
0.968
4.82
14.00
0.968
5.41
13.99
124
0.6
0.5
Spectrum 4
Absorbance
0.4
0.3
Spectrum 1
0.2
0.1
0.0
16600
16800
17000
17200
17400
17600
17800
18000
-1
wave number (cm )
Figure A.12.
The hypersensitive transition spectra of 4.93 mM Nd(III) and 14.3 mM CA with varying
pH, I = 2.00 M NaClO4 and T = 23C. The pH and the oscillator strength of each
125
Table A.10.
Sample
[L]:[M]
pH
P(x106)
2.90
2.43
18.97
2.90
3.08
19.59
2.90
4.34
20.37
2.90
5.47
21.21
126
APPENDIX B.
Eu(III) Laser Induced Fluorescence
127
17276 cm-1
12
Intensity
10
4
17220
17230
17240
17250
17260
17270
17280
17290
17300
17310
17320
-1
wave number (cm )
Figure B.1.
Fluorescence spectrum of 0.296 M Eu(III), I = 2.00 M NaClO4, pH 3.05 and T = 23C.
128
0.8
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Intensity
0.6
0.4
0.2
0.0
17220
17230
17240
17250
17260
17270
17280
17290
-1
wave number (cm )
Figure B.2.
Fluorescence spectra of 1.34 mM Eu(III) with increasing PDA concentration, I = 2.00 M
NaClO4, pH = 5.45 to 5.99 and T = 23C. The concentrations of PDA and the peak
position are listed in Table B.1.
129
Table B.1.
The concentrations of PDA and the peak position of spectra in Figure B.2.
Sample
[PDA], M
[PDA]:[Eu(III)]
peak(cm-1)
9.50E-04
0.709
17273
1.310E-03
0.978
17273
1.750E-03
1.30
17273
3.580E-03
2.67
17273
4.650E-03
3.47
17273
6.680E-03
4.98
17273
130
2.00
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Spectrum 9
Spectrum 10
1.75
Intensity
1.50
1.25
1.00
0.75
0.50
0.25
0.00
17220
17230
17240
17250
17260
17270
17280
17290
-1
wave number (cm )
Figure B.3.
Fluorescence spectra of 1.34 mM Eu(III) with increasing DPA concentration, I = 2.00 M
NaClO4, pH = 5.18 to 5.91 and T = 23C. The concentrations of DPA and the peak
131
Table B.2.
The concentrations of DPA and the peak position of spectra in Figure B.3.
Sample
[DPA], M
[DPA]:[Eu(III)]
peak(s)(cm-1)
1.34E-04
0.100
17260
5.36E-04
0.400
17260, 17252
9.38E-04
0.700
17260, 17252
1.340E-03
1.00
17260, 17252
1.742E-03
1.30
17260, 17252, 17239
2.010E-03
1.50
17260, 17252, 17239
2.278E-03
1.70
17260, 17252, 17239
2.680E-03
2.00
17260, 17252, 17239
3.350E-03
2.50
17239
10
4.020E-03
3.00
17239
132
2.4
2.0
Intensity
1.6
1.2
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Spectrum 9
Spectrum 10
Spectrum 11
Spectrum 12
0.8
0.4
0.0
17220
17230
17240
17250
17260
17270
17280
17290
-1
wave number (cm )
Figure B.4.
Fluorescence spectra of 2.68 mM Eu(III) with increasing CA concentration, I = 2.00 M
NaClO4, pH = 2.28 and 2.77 and T = 23C. The concentrations of CA and the peak
133
Table B.3.
The concentrations of CA and the peak position of spectra in Figure B.3.
Sample
[CA], M
[CA]:[Eu(III)]
peak(s)(cm-1)
2.68E-04
0.100
17266
1.340E-03
0.500
17266
2.412E-03
0.900
17266
2.680E-03
1.00
17266
2.948E-03
1.10
17266
3.484E-03
1.30
17266, 17252
4.556E-03
1.70
17266, 17252
5.628E-03
2.10
17266, 17252
7.236E-03
2.70
17266, 17252
10
8.040E-03
3.00
17266, 17252
11
1.072E-02
4.00
17266, 17252
12
2.680E-02
10.0
17266, 17252
134
APPENDIX C.
1
H NMR Spectroscopy
135
Figure C.1.
H NMR spectrum of PDA, I = 0.50 M NaClO4, pH = 1.10 and T = 25.0C.
136
Figure C.2.
H NMR spectrum of DPA, I = 0.50 M NaClO4, pH = 2.65 and T = 25.0C showing the
2.9 ppm triplet DSS standard peak.
1
137
Figure C.3.
H NMR spectrum of a DPA when [La(III)] = [DPA], I = 0.50 M NaClO4, pH = 3.20 and
T = 25.0C showing the 2.9 ppm triplet and 1.75 multiplet DSS standard peaks.
1
138
Figure C.4.
H NMR spectrum of a DPA when [Lu(III)] = [DPA], I = 0.50 M NaClO4, pH = 3.20 and
T = 25.0C.
139
Figure C.5.
H NMR spectrum of a DPA when [Lu(III)] = [DPA], I = 0.50 M NaClO4, pH = 3.20
and T = 25.0C.
1
140
APPENDIX D.
Crystal Structures
141
Figure D.1.
The structure of PDA determined by crystallography. The ellipsoids indicate the relative
error of the position of all non-hydrogen atoms.
142
Table D.1.
Crystal structure refinement for PDA.
Empirical formula
C7 H13 N O5
Formula weight
191.18
Temperature
298(2) K
Wavelength
0.71073
Crystal system
Monoclinic
Space group
P2(1)/c
a = 10.422(2)
= 90
b = 6.9394(10)
= 96.834(3)
c = 12.4386(19)
= 90
Unit cell dimensions
Volume
893.2(3)
Density (calculated)
1.422 Mg/m3
Absorption coefficient
0.121 mm-1
F(000)
408
Crystal size
0.13 x 0.180 x 0.210 mm3
Theta range for data collection
1.97 to 28.33
Index ranges
-13<=h<=13, -9<=k<=9, -16<=l=<=16
Reflections collected
9106
Independent reflections
2230 [R(int) = 0.0309]
Completeness to theta = 28.33
100.0%
Absorption correction
None
Refinement method
Full-matrix least square on F2
Data / restraints / parameters
2230 / 0 / 175
Goodness-of-fit on F
1.019
Final R indices [I>2sigma(I)]
R1 = 0.0490, wR2 = 0.1138
R indices (all data)
R1 = 0.0606, wR2 = 0.1197
Largest diff. peak and hole
0.340 and 0.166 e.-3
143
Table D.2.
Atomic coordinates (x 10 ) and equivalent isotropic displacement parameters (2 x 103)
for PDA. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
4
U(eq)
C(1)
1922(1)
9134(2)
7768(1)
26(1)
C(2)
3288(1)
9931(2)
7899(1)
35(1)
C(3)
4268(2)
8293(3)
8024(2)
45(1)
C(4)
4015(2)
6944(3)
8944(2)
42(1)
C(5)
2628(1)
6225(2)
8802(1)
30(1)
C(6)
2345(1)
4894(2)
9712(1)
31(1)
C(7)
885(1)
10693(2)
7639(1)
27(1)
N(1)
1726(1)
7905(2)
8717(1)
26(1)
O(1)
244(1)
11048(2)
8375(1)
45(1)
O(2)
769(1)
11549(2)
6722(1)
34(1)
O(3)
1379(1)
5437(2)
10190(1)
39(1)
O(4)
3000(1)
3468(2)
9926(1)
50(1)
O(5)
2148(1)
-153(2)
740(1)
45(1)
144
Table D.3.
Bond lengths [] and angles [] for PDA.
C(1)-N(1)
1.4894(17)
C(1)-C(2)
1.519(2)
C(1)-C(7)
1.5245(19)
C(2)-C(3)
1.524(2)
C(3)-C(4)
1.525(2)
C(4)-C(5)
1.519(2)
C(5)-N(1)
1.4932(17)
C(5)-C(6)
1.517(2)
C(6)-O(4)
1.2137(18)
C(6)-O(3)
1.2853(18)
C(7)-O(1)
1.2198(17)
C(7)-O(2)
1.2787(17)
N(1)-C(1)-C(2)
109.82(11)
N(1)-C(1)-C(7)
109.13(11)
C(2)-C(1)-C(7)
113.36(12)
C(1)-C(2)-C(3)
110.32(13)
C(2)-C(3)-C(4)
111.18(14)
C(5)-C(4)-C(3)
111.20(13)
N(1)-C(5)-C(6)
110.58(11)
N(1)-C(5)-C(4)
109.53(12)
C(6)-C(5)-C(4)
112.36(12)
O(4)-C(6)-O(3)
126.09(14)
O(4)-C(6)-C(5)
120.38(13)
O(3)-C(6)-C(5)
113.53(12)
O(1)-C(7)-O(2)
124.98(13)
O(1)-C(7)-C(1)
120.57(12)
O(2)-C(7)-C(1)
114.45(12)
C(1)-N(1)-C(5)
111.03(11)
145
Table D.4.
Anisotropic displacement parameters (2 x 103) for PDA. The anisotropic displacement
factor exponent takes the form: -22[h2 a*2U11 + + 2 h k a*b*U12].
U11
U22
U33
U23
U13
U12
C(1)
28(1)
25(1)
25(1)
2(1)
6(1)
1(1)
C(2)
28(1)
36(1)
43(1)
8(1)
8(1)
-1(1)
C(3)
29(1)
51(1)
59(1)
18(1)
14(1)
5(1)
C(4)
28(1)
48(1)
51(1)
16(1)
7(1)
7(1)
C(5)
32(1)
28(1)
31(1)
3(1)
6(1)
5(1)
C(6)
32(1)
29(1)
30(1)
1(1)
1(1)
-2(1)
C(7)
26(1)
26(1)
29(1)
-2(1)
4(1)
0(1)
N(1)
23(1)
26(1)
28(1)
1(1)
5(1)
0(1)
O(1)
50(1)
46(1)
42(1)
5(1)
21(1)
17(1)
O(2)
39(1)
34(1)
30(1)
3(1)
5(1)
10(1)
O(3)
44(1)
38(1)
37(1)
9(1)
15(1)
3(1)
O(4)
50(1)
39(1)
62(1)
19(1)
13(1)
11(1)
O(5)
56(1)
35(1)
45(1)
-2(1)
11(1)
4(1)
146
Table D.5.
Hydrogen coordinates ( x 10 ) and isotropic displacement parameters (2 x 103) for PDA.
4
U(eq)
H(1)
1814(15)
8310(20)
7161(14)
31(4)
H(2)
3398(16)
10710(30)
7241(14)
39(4)
H(3)
3386(16)
10740(30)
8539(14)
40(5)
H(4)
5120(20)
8790(30)
8173(16)
56(6)
H(5)
4193(19)
7600(30)
7328(18)
57(6)
H(6)
4554(19)
5870(30)
8993(15)
53(5)
H(7)
4153(17)
7560(30)
9652(16)
47(5)
H(8)
2455(16)
5540(20)
8126(15)
35(4)
H(9)
929(16)
7480(30)
8643(13)
33(4)
H(10)
1885(16)
8630(20)
9372(14)
38(4)
H(11)
1220(30)
4790(40)
10670(20)
19(9)
H(12)
940(90)
10880(140)
6180(90)
200(50)
H(13)
2330(30)
1050(40)
600(20)
82(8)
H(14)
1390(30)
-270(40)
980(20)
78(8)
147
Figure D.2.
The structure of DPA determined by crystallography. The ellipsoids indicate the relative
error of the position of all non-hydrogen atoms.
148
Table D.6.
Crystal data and structure refinement for DPA.
Empirical formula
C9 H13 N O6
Formula weight
231.20
Temperature
298(2) K
Wavelength
0.71073
Crystal system
Orthorhombic
Space group
Pnma
a = 15.8370(12)
= 90
b = 11.3791(9)
= 90
c = 5.5153(4)
= 90
Unit cell dimensions
Volume
993.92(13)
Density (calculated)
1.545 Mg/m3
Absorption coefficient
0.131 mm-1
F(000)
488
Crystal size
0.150 x 0.150 x 0.400 mm3
Theta range for data collection
2.57 to 28.30
Index ranges
-21<=h<=21, -15<=k<=15, -7<=l=<=7
Reflections collected
9812
Independent reflections
1292 [R(int) = 0.0732]
Completeness to theta = 28.33
99.8%
Absorption correction
None
Refinement method
Full-matrix least square on F2
Data / restraints / parameters
1292 / 0 / 112
Goodness-of-fit on F
0.890
Final R indices [I>2sigma(I)]
R1 = 0.0500, wR2 = 0.1263
R indices (all data)
R1 = 0.0590, wR2 = 0.1337
Extinction coefficient
0.000(3)
Largest diff. peak and hole
0.434 and 0.260 e.-3

149
Table D.7.
Atomic coordinates (x 10 ) and equivalent isotropic displacement parameters (2 x 103)
for DPA. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
4
U(eq)
C(1)
4605(1)
2500
7845(5)
33(1)
C(2)
5124(1)
3590(1)
8353(3)
28(1)
C(3)
5947(1)
3594(1)
6910(3)
20(1)
C(4)
6448(1)
4684(1)
7587(3)
25(1)
C(5)
7291(1)
2500
6107(3)
23(1)
C(6)
7252(1)
2500
3352(4)
22(1)
N(1)
6459(1)
2500
7414(3)
18(1)
O(1)
6180(1)
5597(1)
6355(3)
41(1)
O(2)
6982(1)
4714(1)
9120(2)
42(1)
O(3)
6564(1)
2500
2299(2)
31(1)
O(4)
7971(1)
2500
2341(3)
29(1)
150
Table D.8.
Bond lengths [] and angles [] for DPA.
C(1)-C(2)
1.5143(19)
C(1)-C(2)#1
1.5143(19)
C(2)-C(3)
1.527(2)
C(3)-N(1)
1.5110(15)
C(3)-C(4)
1.5192(18)
C(4)-O(2)
1.1963(18)
C(4)-O(1)
1.3115(17)
C(5)-N(1)
1.501(2)
C(5)-C(6)
1.521(3
C(6)-O(3)
1.235(3)
C(6)-O(4)
1.267(3)
N(1)-C(3)#1
1.5110(15)
C(2)-C(1)-C(2)#1
110.02(18)
C(1)-C(2)-C(3)
111.65(14)
N(1)-C(3)-C(4)
110.34(11)
N(1)-C(3)-C(2)
111.10(12)
C(4)-C(3)-C(2)
108.64(11)
O(2)-C(4)-O(1)
124.90(13)
O(2)-C(4)-C(3)
124.48(13)
O(1)-C(4)-C(3)
110.52(12)
N(1)-C(5)-C(6)
116.41(16)
O(3)-C(6)-O(4)
125.82(19)
O(3)-C(6)-C(5)
120.34(18)
O(4)-C(6)-C(5)
113.84(18)
C(5)-N(1)-C(3)#1
112.48(9)
C(5)-N(1)-C(3)
112.48(9)
C(3)#1-N(1)-C(3)
110.91(14)
Symmetry transformations used to generate equivalent atoms: #1 x, -y+1/2,z.

151
Table D.9.
Anisotropic displacement parameters (2 x 103) for DPA. The anisotropic displacement
factor exponent takes the form: -22[h2 a*2U11 + + 2 h k a*b*U12].
U11
U22
U33
U23
U13
U12
C(1)
22(1)
26(1)
51(2)
1(1)
C(2)
26(1)
21(1)
36(1)
-4(1)
2(1)
4(1)
C(3)
26(1)
14(1)
21(1)
-3(1)
2(1)
C(4)
29(1)
18(1)
26(1)
-1(1)
-1(1)
-1(1)
C(5)
22(1)
24(1)
23(1)
-1(1)
C(6)
32(1)
12(1)
22(1)
2(1)
N(1)
22(1)
15(1)
16(1)
-1(1)
O(1)
45(1)
16(1)
61(1)
7(1)
-21(1)
-6(1)
O(2)
59(1)
26(1)
41(1)
1(1)
-23(1)
-10(1)
O(3)
36(1)
38(1)
18(1)
-2(1)
O(4)
37(1)
16(1)
35(1)
14(1)
152
Table D.10.
Hydrogen coordinates ( x 10 ) and isotropic displacement parameters (2 x 103) for DPA.
4
U(eq)
H(1)
4109(19)
2500
8850(50)
44(7)
H(2)
6500(16)
6180(20)
6850(40)
51(6)
H(6)
4818(12)
4294(17)
7930(30)
30(5)
H(7)
5260(11)
3640(15)
10070(30)
27(4)
H(8)
4427(17)
2500
6100(50)
41(7)
H(9)
7578(11)
3206(15)
6660(30)
26(4)
H(10)
5835(11)
3586(13)
5240(30)
16(4)
H(11)
6557(15)
2500
9020(50)
26(6)
153
APPENDIX E.
Previously Published Data From This Work
154
Applications of the Judd-Ofelt Theory in Lanthanide-Chelidamic Acid Complexation.

Gergory R. Choppin and Glenn A. Fugate, Molecular Physics. 101(7), 935-939, 2003.
Department of Chemistry, Florida State University, Tallahassee, Florida 32306
Abstract
The coordination chemistry of trivalent lanthanides with chelidamic acid was
studied using fluorescence and absorption spectroscopic methods. The speciation was
determined using Eu(III) fluorescence techniques. The stability constants and the
oscillator strengths were determined for the Ho(III) complexes from absorbance
measurements of a Ho(III) hypersensitive transition. The lanthanide coordination
chemistry of chelidamic acid and dipicolinic acid is compared.
Introduction
The model to calculate the oscillator strength of lanthanide ff electronic
transitions developed by Judd1 and Ofelt2 has been used to better characterize band
assignments of the f-elements as it accounts for hypersensitive bands that exhibit a
strong sensitivity to the environment about the ion. Several analytical techniques take
advantage of these hypersensitive bands to obtain useful information on the coordination
of f-element cations in complexes.
Many lanthanides exhibit hypersensitivity, and, in particular, Nd(III), Er(III) and
Ho(III) exhibit relatively narrow hypersensitive bands corresponding to 5I85F1, 5G6,
4
I13/22H11/2 and 4I9/22G7/2,4G5/2 transitions, respectively. The effects of ligands on
these hypersensitive transitions have been used to calculate the coordination number3 and
155
solvent effects on coordination4. The fluorescence of Eu(III) and Tb(III) can also provide
useful data on the complexes of these cations. The 5D07FJ transitions of Eu(III) and the
5
D47FJ transitions of Tb(III) (J=0,1,2,3,4,5 or 6) can be used to obtain structural
information on complexes of these ions such as the number of different metal binding
sites, the distance between those sites, the local symmetry around the metal, the ligand
exchange rates and the number of water molecules still bound to the metal in the
complex5. Stability constants can be obtained from spectroscopic fitting of titration data
of fluorescence measurements6.
Chelidamic acid, Figure 1, is a commercially available molecule whose
complexes with f-elements have not been extensively characterized in the literature.
Some of the techniques mentioned above have been utilized in this study to clarify the
nature of the lanthanide complexes with this molecule.
Experimental
The Eu2O3 and Ho2O3 (99.99%, Aldrich Chemical) were dissolved in a slight
excess of perchloric acid (ACS reagent, Fisher Scientific) followed by repeated
evaporation to near dryness and redissolution to prepare solutions of Eu(ClO4)3 and
Ho(ClO4)3. The lanthanide ion concentration was determined by titration with
ethylenediaminetetraacetic acid (standard solution, Aldrich Chemical) at pH 4.5 (acetate
buffer) with xylenol orange as indicator. A few drops of pyridine were added to enhance
the color transition of the indicator7.
Chelidamic acid (97%, Aldrich Chemical), 2,6-dicarboxy-4-hydroxypyridine, was
used without further purification. Sodium perchlorate (ACS reagent, Aldrich Chemical)
156
solutions were filtered through 0.45 m nylon membrane filter and used without further
purification.
Eu(III) fluorescence experiments were performed in a 1 cm quartz cell using a
Nd-YAG laser (Quanta Ray DCR 2A, Spectra Physics) coupled to a pumped dye laser
(Quanta Ray PDL2, Spectra Physics). The excitation monochromator (Jarell-Ash) was
controlled with a computer interfaced stepper motor allowing scanning of the dye laser
emission throughout the entire range of the emission wavelength of the dye. The
fluorescence was detected perpendicular to the incident beam using a Hamamatsu R928
photomultiplier tube. Excitation spectra were collected as the average of 50 pulses per
point over a range of 17210 to 17320 cm-1 in 1 cm-1 increments using software written in
the department. A typical spectrum is shown in Figure 2. Lifetime measurements were
performed at a fixed wavenumber corresponding to peak maxima using an oscilloscope
that transferred the data to computer. This data was the average decay curve from 1000
fluorescence decays.
Ho(III) hypersensitive transitions were monitored in 10 cm glass cells using an
OLIS converted dual beam Cary 14 UV-visible spectrophotometer. A reference sample
of water was measured for background correction. The spectra were measured over the
range of 425 to 475 nm in 1 nm increments as shown in Figure 3. Each data point is the
averaged value of 50 readings.
Results
Addition of the chelidamate ligand to a solution of Eu(III) produced a
fluorescence spectrum with peaks corresponding to the different species in the solution.
157
More dehydrated species have emissions shifted to lower wavenumbers. At room

temperature in pH 2.2, 0.5 M sodium perchlorate medium and chelidamic acid
concentrations from 1 to 3 times that of Eu(III), the spectra show only two peaks, Figure
2. This indicates that only two complexes of Eu(III) and chelidamate exist under these
conditions.
The change in the inner coordination sphere of the Eu(III) cation was calculated
using two methods with the results summarized in Table 1. The change in the peak
position can be used to estimate the number of ligand coordinations to the complexed
Eu(III) ion from the equation8:
CNL = 0.237 + 0.628
where CNL is the number of ligand coordinations and is change in the peak position
relative to the 17276 cm-1 peak of Eu(H2O)93+. This analysis shows that each
chelidamate ligand is tridentate in both the Eu(III)L and Eu(III)L2 complexes. A peak at
17239 cm-1 was seen which most likely corresponds to the Eu(III)L3 complex. This peak
never gains a significant intensity and typically occurred when the chelidamate
concentration was more than five times greater than the Eu(III) concentration.
If we assume a constant total coordination number of Eu(III), the number of
coordination sites occupied by the ligand can be determined indirectly from the number
of water molecules in the inner coordination sphere of the coordinated cation. The
fluorescence lifetimes of the individual peaks in the spectra were shown by Horrocks and
Sudnick9 to allow the calculation of the number of water molecules in the inner
coordination sphere by measurement in water and deuterium oxide. However, since the
fluorescence lifetime decay constants in deuterium oxide exhibit trivial changes in
158
comparison to the decay constants in water solutions, the decay constant in deuterium
oxide can be treated as a constant in the equation10:
nH2O = 1.07kobs 0.62
where nH2O is the number of water molecules in the inner hydration sphere of the Eu(III)
ion and kobs is the luminescence decay constant for the species. The luminescence
lifetime decay constants were measured from the first order exponential fit of the decay
curve. The first complex displaces 4 water molecules from the inner hydration sphere to
form a tridentate complex. The ML2 complex has 6 waters displaced in the hydration
sphere, consistent with the displacement of 3 water molecules by each of the tridentate
ligands. The ML3 species was not obtained in significant concentration to measure the
luminescence decay curve.
The oscillator strength, Pe, can be calculated by the equation11:
Pe = 4.3198E - 09 ( )d
i
where is the molar absorptivity at the energy (cm-1). The integral can be
approximated by the equation12:
( )d =
S
[Ho(III)]t c
where S is the area of the hypersensitive peak in units of absorbancecm-1 obtained by

integration using GRAMS/32 version 3.04 software, [Ho(III)]t is the total concentration
and c is the path length of the cell in cm. The plot of Pe versus the ligand : metal
concentration ratio can be resolved into 3 linear regions, Figure 4. The first region occurs
when the chelidamate ligand has a lower concentration than Ho(III), limiting
complexation to the formation of the Ho(III)L complex. The second region occurs where
159
the ligand concentration is greater than that of Ho(III), allowing formation of the
Ho(III)L2 species. Finally, at some point after the chelidamate concentration exceeds
twice that of the metal ion, the slope of this region becomes near zero, indicating that no
additional coordination is occurring. These results are in agreement with the Eu(III)
fluorescence data mentioned above in which only 2 species were seen under similar
experimental conditions. A linear fit of Pe as a function of the chelidamate : Ho(III) ratio
where the ligand concentration is sufficiently low that only the Ho(III)L complex is
present can be used to determine the oscillator strength of the Ho(III) aqua ion from the
intercept and to calculate the oscillator strength of the first complex. The oscillator
strength of the Ho(III)L2 species is the constant value of Pe when the concentration of
ligand exceeds twice that of the metal. From the oscillator strengths, the mole fraction of
the species can be calculated, allowing evaluation of a conditional stability constant for
the both complexes. The oscillator strengths and conditional stability constants of the
complexes are listed in Table 2.
Discussion
Dipicolinic acid has been used for comparison to chelidamic acid as it has a
similar structure, lacking only the 4-hydroxy group13,14,15. Albin and Horrocks16 used
Eu(III) fluorescence to study chelidamic acid complexes and found species with peaks at
17265, 17251 and 17235 cm-1 which are in excellent agreement with the peak positions in
this study. However, no other findings or calculations on this ligand were offered in
reference 16. Horrocks and Sudnick17 studied the formation of Eu(III) complexes with
dipicolinic acid and found ML, ML2 and ML3 species that showed a stepwise removal of
160
3 water molecules from the inner hydration sphere upon the coordination of each ligand.
The removal of 4 water molecules in the ML species of chelidamic acid can be attributed
to the slightly larger bite size of the coordination site due to the aliphatic-aromatic
equilibrium. If the second chelidamate ligand displaces 4 water molecules as the first
ligand, the residual nH2O would be 1. Eu(III) has 3 coordinated waters in the inner
hydration sphere in the ML2 species which, based on a total coordination number of 9,
indicates that only 6 water molecules were released. This reduction of water molecules
displaced by coordination of a second ligand can be explained by the repulsion between
the negative charges of the chelidamate ligands causing an increase in the distance
between the metal and both coordinating ligands, to reduce steric crowding. The ML3
complex was observed at very small concentrations species even when the ligand
concentration was five times greater than that of the metal. The larger bite size of
chelidamate probably introduces a steric effect that reduces the strength coordination of a
third ligand, inhibiting the formation of the ML3 species seen in the dipicolinic acid
study.
Fellows and Choppin18 report values for the oscillator strengths of 5.98 x 10-6 for
the Ho(III) aquo ion and 14.26 x 10-6 for the ML complex with dipicolinic acid. The
value for HoChel+1 is slightly smaller than that of HoDP+1 which may reflect the larger
chelate bite of the chelidamate ligand.
Grenthe19 reported stability constants for dipicolinic acid complexes with
lanthanide ions. The stability constants for the Ho(III) complexes are log 101 = 8.72, log
102 = 16.23 and log 103 = 22.08 at 20 C in 0.5 M perchlorate medium. The conditional
constants found in this study for chelidamic acid are significantly lower. Bag et al.13
161
showed that the acid dissociation constant of the hydroxy group is significantly reduced
when the chelidamate ligand is bound to a cation even though this functional group is not
involved in the coordination of the metal. Their study determined that the hydroxy group
has a pKa of 10.8 for the free ligand which is reduced to 5 to 6 in coordinated complexes
and is explained as stabilization of the keto form of the chelidamate. In a subsequent
study, we plan to conduct C13 NMR studies to measure changes in the molecule produced
by coordination to a lanthanide ion if the metal complex is significantly soluble to obtain
spectra. The predominance of the keto form would support the previous conclusion from
Eu(III) fluorescence that the chelidamate has a larger bite size than the dipicolinate as the
ligand would show increased aliphatic nature due to the ketonic nature of the former
when complexed. A result would be an increased total negative charge over the
coordination site which agrees with the larger stability constants for the 1:1 complex
relative to that for the dipicolinate 1:1 complex as seen in comparison of the 1:1 stability
constants of the alkaline earth cations20. This would also account for the ML3 species of
chelidamate being much weaker that of the dipicolinate due to the repulsion of this
increased net charge of the 3 chelidamate ligands and the greater steric crowding by their
larger bite size.
Anderegg14 reported that different metal complex formation constants were
obtained for the protonated and deprotonated species of the chelidamate ligand. The
trends and variations seen among the constants of different metals (none were Ln(III))
did not follow any pattern. The conditional constants we report are, quite possibly, some
mixture of an aromatic structure with the negative charge localized on the phenol group
and an aliphatic structure with the charge localized on the amine. Andereggs study
162
appears to treat the complexed ligand as being only the aromatic form, with the
deprotonation resulting in the negative charge being localized at the phenolic oxygen.
Conclusion
The Judd-Ofelt theory provides a useful basis to predict the ff electronic

transition spectra of the lanthanide elements and to explain the hypersensitivity found in
some of the lanthanides. Many of these lanthanide hypersensitive spectroscopic peaks
can be used to give useful information of the environment surrounding the metal ion and
to determine stability constants for lanthanide complexes.
Acknowledgment
This research was supported by a contract from USDOE-OBES Division of Chemical

Sciences.
163
Table 1. Eu(III) fluorescence of chelidamic acid complexes.

peak
CNL
nH2O
species
17276 cm-1
Eu(H2O)93+
17265 cm-1
3.2 0.5
4.48 0.34
EuL(H2O)5+
17251 cm-1
6.6 0.5
2.79 0.27
EuL2(H2O)3-1
17239 cm-1
9.4 0.5
EuL3-3
Table 2. Ho(III) Oscillator Strengths of chelidamic acid complexes.

species
Oscillator Strength (x106)
Ho3+
5.934 0.035
HoL+
13.457 0.032
5.41 0.75
HoL2-
23.438 0.029
9.05 0.88
164
log n
Figure 1.
O
N
OH
OH
O
OH
N
OH
O
OH
Figure 1. Chelidamic acid.
165
Figure 2.
80
intensity
60
40
20
0
17220
17240
17260
17280
17300
17320
-1
wavenumber (cm )
Figure 2. Eu(III) laser induced fluorescence spectra of 1 : 1, 2 : 1 and 3 : 1 ratios

of [chelidamic acid] : [Eu(III)] in pH 2.2, 0.5 M sodium perchlorate at room temperature.
166
Figure 3.
0.4
Absorbance
0.3
0.2
0.1
0.0
430
440
450
460
470
wavlength (nm)
Figure 3. Spectra of the Ho(III) hypersensitive electron transition of 1 : 0, 1 : 0.36,

1 : 0.67 and 1 : 1.03 ratios of [Ho(III)] : [chelidamic acid] in pH 4.4, 2.0 M sodium
perchlorate at room temperature.
167
Figure 4.
26
24
22
20
Pe (x 106)
18
y = 8.45(0.23)x + 5.18(0.33)
R2 = 0.9963
16
14
12
10
y = 7.58(0.06)x + 5.93(0.02)
R2 = 0.9996
8
6
4
0.0
0.5
1.0
1.5
2.0
2.5
3.0
[chelidamic acid] : [Ho(III)]
Figure 4. The linear relationship of the area of the oscillator strength, Pe, and the
[chelidamic acid] : [Ho(III)] ratio. Solid symbols represent data used in the separate
linear fits. The standard error of each fitting constant is given in parentheses.
168
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20
Critical Stability Constants of Metal Complexes Database. 3.0 ed., A. E. Martell, R. M. Smith and R. J.
Motekaitis, eds., Texas A&M University: College Station, TX, 1997.
2
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176
BIOGRAPHICAL SKETCH
Glenn Andrew Fugate was born in Rogersville, Tennessee, on 6 November 1973 to Nila
Hamblen Fugate and Clay Reece Fugate and has one brother, David Lee Fugate. He
received a Bachelors degree in Chemistry from Tennessee Technological University at
the end of the spring semester of 1996.
While attending Tennessee Technological
University, he performed undergraduate research for Dr. Thurston E. Banks and Dr. Dale
D. Ensor of TTU and spent two internships working for Dr. Kenneth L. Nash at Argonne
National Laboratory. Glenn A. Fugate attended the American Chemical Society Nuclear
Division Nuclear Chemistry Summer School in 1994 and was awarded the Charles D.
Coryell award in 1995 for undergraduate research in nuclear related areas. He attended
Florida State University from 1996 to 2003.
177

Complexation With Aminopolycarboxylic Acids

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Complexation of f-Elements with

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THE FLORIDA STATE UNIVERSITY

COMPLEXATION OF f-ELEMENTS WITH

A Dissertation submitted to the

2.1.7.2 Ligands Solutions.............................................................19

3.1.3 Lanthanide(III) Complex Stability Constant Determination .......34

BIOGRAPHICAL SKETCH ..............................................................................176

Table 4.1: The concentration acid dissociation constants for PDA, T =

Figure 1.1: Structures of NTA, EDTA and DTPA .............................................9

LIST OF ABBREVIATIONS AND SYMBOLS

calculated coordination number of the ligand

nuclear Overhauser effect

oscillator strength of the metal aquo ion

oscillator strength of the ML complex

oscillator strength of the ML2 complex

1.1 Statement of Problem

Typically these compounds are straight chain aliphatic

Aminopolycarboxylate ligands were found to have better

Other studies compared lanthanide(III)

Ethylene groups promote the formation of a 5 member ring

Additionally, the effects of

Several studies have characterized the lanthanide(III) coordination chemistry of

An inner sphere complex forms through an Eigen

The increased covalency results in actinide elements having

Mssbauer spectroscopy measurements have

shown increased shift values as the actinide oxidation state is increased46.

Solvent extraction and synergistic solvent extraction studies have also

These transitions are termed hypsersensitive and have the

following characteristic change in term symbols: S = 0 or 2, |L| 2 and |J| 251.

Luminescence radiation emissions occur because

lanthanide-ligand radiationless de-excitation processes are relatively ineffective. The

The O-D oscillator does not quench the luminescence as

Most aliphatic aminocarboxylate ligands previously studied are

The size selectivity of PDA across the

The coordination nature of ligands with similar

Structures of NTA, EDTA and DTPA .

2.1 Chemical Reagents

concentrations indicated that the purity of each ligand was 99%.

2.1.3.3 2,6-Dicarboxypipepridine-N-acetic Acid

The perchloric acid stock

solutions were standardized by titration with standardized sodium hydroxide solutions

590 tetrafluoroborate (Exciton) and Rhodamine 610 perchlorate (Exciton) in methanol

The excitation monochromator (Jarell-Ash) was

The stability of the laser was

The system was

Temperature readings were made with a YSI model

SP033-108 thermistor connected to a Keithley model 181 nanovoltmeter. The Peltier

The instrument was

interfaced to a computer and managed by software written by Dr. M. Caceci76 that

A 0.1 mV value was selected as the maximum difference between

consecutive readings for all experiments.

was 30 s. Standardization titrations were conducted once for every 1 to 3 experimental

Experiments were performed similarly to those of the pH titration

These experiments were

performed on solutions of PDA and DPA at pH 2.00 and 11.00.

This decoupling removed

H spectrum was collected while an individual 1H peak was suppressed.

3.1 Potentiometric Titrations

3.1.1 Electrode Calibration

The concentration of the hydrogen ion was