Chapter 1 Ultraviolet/Visible Spectroscopy

Introduction f S I t d ti of Spectroscopy t
The structure of new compounds that are isolated from natural sources or prepared in the p p lab must be determined (and/or verified).
Chemical analysis (Classical methods) y ( ) Spectroscopy (Modern techniques)

Spectroscopic techniques are non-destructive and generally require small amounts of sample sample.

Types of Energy in Each Region of the yp gy g Electromagnetic Spectrum

Region of Spectrum
X-rays Ultraviolet/Visible Infrared Microwave Radiofrequencies

Energy Transitions
Bond Breaking Electronic Vibrational Rotational Nuclear Spin (Nuclear Magnetic Resonance) Electron Spin (Electron Spin Resonance)

Four common spectroscopic techniques used to determine structure:

Ult i l t S Ultraviolet Spectroscopy t Infrared Spectroscopy (IR) Nuclear Magnetic Resonance Spectroscopy (NMR) Mass Spectrometry (MS or Mass Spec)

 Ult i l t S Ultraviolet Spectroscopy t

Observes electronic transitions
Provides information on the electronic bonding in a molecule

 Infrared spectroscopy:
Used to determine the functional groups present in a molecule

Mass spectrometry
B k molecule i t Breaks l l into fragments
Analysis of the masses of the fragments gives f th f t i MW and clues to the structure of the molecule

 N l Nuclear M Magnetic R ti Resonance S Spectroscopy t

Observes the chemical environment of the hydrogen (or carbon) atoms in the molecule
Helps provide evidence for the structure of the carbon skeleton and/or the alkyl groups present k l t d/ th lk l t

1H

NMR of CH3CH2OH

13C

NMR of CH3CH2OH

1.1 1 1 Principle of UV Light Absorption

Ultraviolet light: wavelengths between 190 and 400 nm Visible light: wavelengths between 400 and 800 nm Ultraviolet/visible spectroscopy involves the absorption of ultraviolet light by a molecule causing the promotion of an electron from a ground electronic state to an excited electronic state.

Principle of UV p

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There are several types of electronic transitions available to a molecule including:

to (alkenes) to ( lk (alkenes, carbonyl compounds, alkynes, azo b l d lk compounds) n to ( (oxygen, nitrogen, sulfur, and halogen it lf dh l compounds) n to ( b (carbonyl compounds) l d)

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Instrument frame

12

Spectrometer

Multichannel photodiode array

Ultraviolet/Visible Spectroscopy
Hewlett-Packard 8452a Diode Array Spectrophotometer

1.2 Electronic Excitations

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Vibrational levels

Electronic excited state

Vibrational levels

Electronic ground state

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1.3 1 3 The Origin of UV Band Structure

A UV Absorption Band at Room Temperature (A) and at Lowered Temperature (B)

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1.4 the absorption lawthe Beer-Lambert Law

I log = .l.c I
0 10

Io = the intensities of the incident light I = the intensities of the transmitted light l = the path length of the absorbing in centimetres c = the concentration in moles per litre log ( I / I ) is called the absorbance or optical density; is known as the molar extinction cofficient
10 0

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1.5 Presentation of Spectra

= 230nm;
max

log = 4.2
3.1 2.9

272 282

Ultraviolet Spectrum of Benzoic A id i C l h Ult i l t S t fB i Acid in Cyclohexane

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1.6 C Choice of S f Solvents

So e so ve s Some solvents used in ultraviolet spectroscopy u v o e spec oscopy
Solvent
Acetonitrile Water Cyclohexane Hexane Methanol Ethanol Ether Methylene dichloride Chloroform Carbon tetrachloride

Minimum wavelength for 1 cm cell, nm ll

190 191 195 201 203 204 215 220 237 257

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The first criterion for solvent

A good solvent should not absorb ultraviolet radiation in the same region as the substance whose spectrum is being determined determined. Usually solvents which do not contain conjugated systems are most suitable f thi purpose, although t t it bl for this lth h they vary as to the shortest wavelength at which they th remain t i transparent t ultraviolet radiation. t to lt i l t di ti The solvents most commonly used are water, 95% ethanol, and n-hexane.
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A second criterion ( the effect of a solvent on the fine structure of an absorption band)

Ultraviolet Spectra of Phenol in Ethanol and in Isooctane

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Large energy lowering caused by g y solvent interaction

The effect of a polar solvent on a transition

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A third property of a solvent

The ability of a solvent to influence the wavelength of ultraviolet light which will be absorbed. Polar solvents may not form hydrogen bonds as readily with excited states as with ground states of polar solvents. Transitions of the n * type are shifted to shorter wavelengths by polar solvents. On the other hand, in some cases the excited states may form stronger hydrogen bonds than the corresponding ground state. In such cases, a polar solvent would shift an absorption to longer wavelength, since the energy of the electronic transition would be decreased. Transitions of the * type are shifted to longer wavelengths by polar solvents.
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Solvent Shifts on the Transition in Acetone

n *
Solvent Sl t H2O 264.5 CH3OH C2H5OH CHCl3 270 272 277 C6H14 279

, nm
max

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1.7 the Effect of Conjugation

Ultraviolet Spectra of Dimethylpolyenes, CH3(CH=CH)nCH3 ; A, n=3; B, n=4; C, n=5

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Conjugation of two chromophores not only results in a bathochromic shift, but it also increases the intensity of the b th absorption. ti The Effect of Conjugation on Electronic Transitions
Alkenes Ethylene 1,3-Butadiene 1,3,5-Hexatriene Carotene -Carotene (11 double bonds) Ketones Acetone * n * 3-Buten-2-one * n * max (nm) 175 217 258 465 15,000 15 000 21,000 35,000 125,000 ,

189 280 213 320

900 12 7,100 27
27

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1.8 the Effect of Conjugation on Alkenes

Formation of the Molecular Orbitals for Ethylene

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Fig. 1-13 Comparison of th Fi 1 13 A C i f the Molecular Orbital Energy Levels and Energy of the * Transitions in Eth lene and 1 3 Ethylene 1,3Butadiene

Conjugation makes the energy lower j g gy

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A Comparison of the * Energy Gap in a Series of Polyenes of Increasing Chain Length

The longer the conjugated system, the longer the g j g y , g wavelength of the absorption maximum. 31

the Appearance of the Spectra of some Polyenes

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An extension of the length of the conjugated system

B = -OH, -OR, -X, or NH2 OH OR X NH

E1 E2

Energy Relationships of the New Molecular Orbitals and the Interacting System and its Auxochrome

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Overlap of the electrons

Hyperconjugation

Quasi-resonance structures

The net effect is an extension of the system .

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1.9 the Effect of conformation and Geometry on Polyene Spectra

All-trans polyenes show only the 2 3* transition In polyenes with one or more cis double bonds the 2 4* bonds, transitions may become allowed called cis band. Any molecule which retains a center of symmetry, even when possessing several cis d bl b d will not show th cis i l i double bonds, ill t h the i band. 35

Spectra of isomeric -carotenes, showing the development of the cis band.

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Empirical rules for caluclating UV/Vis Absorptions

Woodward-Fieser Rules for Dienes A. Woodward's Rules for Conjugated Carbonyl Compounds B. Mono-Substituted Benzene Derivatives C. Di-Substituted Benzene Derivatives D. Benzoyl Derivatives
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1.10 the Woodward-Fieser Rules for Dienes

conjugated di j t d dienes
* transition =20,000 to 26,000 =217 to 245nm Butadiene and many simple conjugated dienes exist in a planar sB t di d i l j t d di i ti l trans conformation. y, y produces bathochromic shifts and Generally, alkyl substitution p hyperchromic effects. With certain patterns of alkyl substitution, the wavelength increases, increases but the intensity decreases. decreases

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Cyclic dienes
The central bond is a part of the ring system, the diene chromophore is usually held rigidly in either the s trans or the s cis conformation s-trans s-cis

Homoannular Diene (s(s-cis) less intense, = 5,000 15,000 intense 5 000 15 000 longer (273nm)

Heteroannular Diene (s(s-trans) more intense, = 12,000 28,000 shorter (234nm)

The actual rules for predicting the absorption of open chain and sixmembered ring diene were first made by Woodward in 1941. Since that time they have been modified by Fieser and Scott as a result of experience with a very large number of dienes and trienes.
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Rules for diene and triene absorption

Value i d t V l assigned to parent heteroannular or open diene th t l di Value assigned to parent homoannular diene Increment for (a) each alkyl substituent or ring residue (b) the exocyclic double bond (c) a double-bond extension (d) auxochrome OCOCH3 OR SR Cl, Br NR2 calc Total
H H C H C H C C H H

214 nm 253 nm 5 nm 5 nm 30 nm 0 nm 6 nm 30 nm 5 nm 60 nm
H C C H H

H 3C H 3C C H 3C C

transoid: observed: b d

214 nm 217 nm

transoid: alkyl groups: observed:

214 nm 3 5 = 15 229nm 228 nm

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CH3
a A a B a

CH3

Exocyclic Double Bond

CH CH C 3C 2O

transoid: 214 nm ring residues: 3 5 = 15 exocyclic double bond: 5 234 nm observed: 235 nm
CH3

observed:

240 nm 241 nm
CH3 CH CH3

CH3

cisoid: 253 nm ring residues: 3 5 = 15 exocyclic double bond: 5 273 nm observed: 275 nm

observed:

278 nm 275 nm 41

CH3 CH3

cisoid: 253 nm ring residues: 5 5= 25 double bonds extending g conjugation: 2 30 = 60 exocyclic double bonds: 3 5 = 15 CH3COO: COO : 0 353 nm observed: 355 nm

CH3COO

The Woodward-Fieser rules work well for polyenes with from one to four conjugated double bonds. j g
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1.11 1 11 the Fieser-Kuhn Rules for polyenes

-Carotene, Carotene 11 Double Bonds max= 452 nm(hexane), =15.2 104

Lycopene, 13 Double Bonds (11 Conjugated) y p , ( j g ) max= 474 nm(hexane), =18.6 104
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Empirical Rules for Polyens E ii lR l f P l

(hexane) = 114 + 5M + n(48.0 1.7 n) 16.5R 10 R (hexane) = 1.74 10 n
max endo d 4 max exo

where: M n Rendo Rexo = = = = the number of alkyl substituents the number of conjugated double bonds the number of rings with endocyclic double bonds the number of rings with exocyclic double bonds g y

For example, -Carotene: M = 10 n = 11 Rendo = 2 Therefore: max= 453.3 max= 19.1 104
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Rexo = 0

1.12 1 12 carbonyl compounds; enones b l d

Two i i l T principal uv transition: ii
forbidden 280-290 280 290 nm allowed 190 nm

Substitution by an auxochrome with a lone pair of electrons, such as NR2, OH, OR, NH2, or X, as in amides, acids, esters, or acid chlorides, gives a pronounced hypsochromic effect on the n* transition and lesser bathochromic effect on the * transition. (resonance interaction)
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the Hypsocromic Effect of Lone Pair Auxochromes on the n* Transition of a Carbonyl Group
max
O CH3 C O H

max

Solvent S l t

293 nm 279 235 214 204

12 15 53 60

Hexane Hexane Hexane Water Water

CH 3

C O

CH 3

CH 3
CH3

C
O C

Cl
NH2

O CH 3 C

OCH2CH3

This shift is due primarily to the inductive effect of the oxygen, nitrogen, or halogen atoms. They withdraw electrons from the carbonyl carbon, g y y causing the lone pair of electrons on oxygen to be held more firmly than 46 would be the case in the absence of an inductive effect.

the Spectra of a Series of Polyene Aldehydes If the carbonyl group is a part of a conjugated system of double bonds, both h b h the n* and the * b d are shifted to longer wavelengths. * d h * bands hif d l l h The energy of the n* transition does not decreased as rapidly as that of the * band, which is more intense. If the conjugated chain becomes long enough, the n* band becomes 47 buried under the more intense * band.

the Orbitals of an Enone System Compared to those of the Noninteracting Chromophores

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1.13 Woodwards Rules for Enones

Conjugation of a double bond with a carbonyl group leads to absorption ( = 8,000 8 000 to 20,000), *, at 220 ~ 250 nm, predictable n n*, at 310 ~ 330 nm much less intense ( nm, = 50 to 100), not predictable

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H 3C C H 3C C

O C CH 3

CH3 OCOCH3

CH 3

acyclic enone: CH3: CH3: CH observed:

CH3

215nm 10 24 249nm 249nm

6 membered 6-membered enone: double bond extending conjugation: homocyclic diene -ring residue: observed: b d
O CH3

215nm 30 39 18 302nm 300nm 300

Br

5-membered enone: -ring residue: 2 12= exocyclic double bond: observed:

202nm 24 5 231nm 226nm

5-membered enone: -Br: B -ring residue: 2 12= exocyclic double bond: observed:

202nm 25 24 5 256nm 251nm

1.14 1 14 Solvent Shifts a more detailed examination

1. In most * transitions
( (bathochromic shift, lower energy) gy)
*
E N E R G Y

Large energy lowering caused by solvent interaction

Non-Polar Solvent Polar Solvent

the Effect of a Polar Solvent on a Transition

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The ground state of the molecule is relatively non-polar, and the excited state is often more polar than the ground state. As a result, when a polar solvent is used, it interacts more strongly with the excited state than with the ground state, and the transition is shifted to longer wavelength. g g g

the th ground state d t t the electron density equally distributed, the nuclei of C are shielded the * excited state the electron is promoted, the C becomes electron deficient The excited state interacts more strongly with polar or hydrogen bonding solvents
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2. 2 In most n* transitions n
(hypsochromic shift, higher energy)
*
E N E R G Y
becomes electron deficient

Non-Polar Solvent Polar Solvent

* C* O

} n

Large solvent stabilization due to hydrogen bonding

C O

H O H

the Eff h Effect of a Polar Solvent on an n* T f P l S l * Transition ii The ground state is more polar than the excited state. Hydrogen bonding solvents interact more strongly with unshared electron pairs in the ground state molecule

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1.15 1 15 Aromatic Compounds

Molecular Orbitals and E M l l O bit l d Energy St t f Benzene States for B

184 and 202 nm 255nm

primary bands secondary bands (fine-structure)

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The second primary band (184 nm, =47,000) in vacuum ultraviolet region The 202 nm band is much less intense (=7,400), it corresponds to a forbidden transition The secondary band is the least intense of the benzene bands (=230) ( 230). It corresponds to a symmetry forbidden electronic transition. Ultraviolet Spectrum of Benzene
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A. A Substitutents with Unshared Electrons

Y Y Y Y

The non-bonding electrons can increase the length of g g the system though resonance. The more available these n-electrons are for interaction with the system of the aromatic ring, the greater the shifts will be. (-NH2, -OH, -OCH3, -X) Interactions of this type between the n and electrons usually cause shifts in the primary and secondary benzene absorption bands to longer y p g wavelength. In addition, the presence of n-electrons in these compounds gives the possibility of n* transition.
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If an n-electron is excited into the extended * chromophore, p , the atom from which it was removed becomes electrondeficient, while the system of the aromatic ring acquires an extra electron. This causes a separation of charge in the molecule. The extra electron in the ring is actually in a * orbital.
* Y * Y Y * Y
*

A charge transfer or an electron transfer excited state

With compounds which are acids or bases, pH changes can have a very significant effect on the positions of the primary and secondary bands.
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B. S b i B Substituents capable of -conjugation bl f j i

C O R C O R C O R C O R

Interaction of the benzene ring electrons and the electrons of the substituent can also produce a new electron transfer band. This new band may be so intense as to obscure the secondary band of the benzene system. Notice that the opposite polarity is induced; the ring becomes electron deficient. The effect of acidity or basicity of the solution on such a chromophoric substituent group
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C. Disubstituted benzene Derivatives

A. For para-, two possiblities: . o pa a , wo poss b es: 1. Both groups are electron-releasing or electronwithdrawing, similar to monosubstituted benzenes; 2. One is electron-releasing while the other is electronwithdrawing, enhanced shifting (the magnitude of the shift of the primary band is greater than the sum of the shifts due to the individual group.)
O H2N N+ O H2N O N+ O

resonance interactions
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Empirical Rules for Benzoyl Derivatives

O C R

Parent chromophore: y g R = Alkyl or ring residue R=H R = OH or OAlkyl Increment for each substituent: Alkyl -Alkyl or ring residue -OH,-OCH 3 ,or OAlkyl -O O o-,mo- mpo-,mpoo mpo-,mpo-,mpo-,m, po-,mppo-,mp-

246 250 230 3 10 7 25 11 20 78 0 10 2 15 13 58 20 45 73 20 85

-Cl -Br -NH 2 -NHCOCH 3 -NHCH 3 NHCH -N(CH 3 ) 2

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Br
O HO O HO OH C OH

parent chromophore: 246nm o-ring residue: i id 3 m-Br: 2 251nm observed: 253nm

parent chromophore: 230nm m-OH: 2 7 = 14 p-OH: 25 269nm observed: 270nm

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Application of UV
1.To obtain the information of conjugation, 2.Qualification 2 Qualification analysis 3.Quantitative analysis: A=bc

Example spectra

Example spectra

Apracticalguide:Exercises Whatdoyoulookforinanultraviolet spectrum?

A single band of low intensity (10 to 100) in the region 250 360nm, 360nm with no major absorption at shorter wavelengths (200250nm) n*
Asimple,orunconjugated,chromophore(containsanO,N,orS): A i l j d h h ( i O N S) C=O,C=N,N=N,NO2,COOR,COOH,orCONH2

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Two bands of medium intensity (=1,000 to 10,000), both with ( 1,000 max above 200 nm an aromatic system
A good d l of fine structure in the longer wavelength band (in non-polar A d deal f fi t t i th l l th b d (i l solvents only). Substituent on the aromatic rings will increase the molar absorptivity above 10,000. 10 000 In polynuclear aromatic substances, a third band will appear near 200 nm.

Bands of high intensity (=10,000 to 20,000), above 210 nm unsaturated ketone or a diene or polyene

an ,-

The longer the length of the conjugated system, the longer the observed wavelength will be. For dienes using the Woodwood fieser rules dienes, Woodwood-fieser More than four double bonds, using Fiese-Kuhn rules

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Simple ketones, acids, esters, amides, and other compounds p , , , , p containing both system and unshared electron pairs, will show two absorptions: n* at longer wavelength (>300nm low intensity) (>300nm, * at shorter wavelength (<250nm, high intensity)
With conjugation (enones), the max of the * band moves to linger wavelengths , Woodwards rules above 10,000, bury the weaker n* transition y ,-unsaturated esters and acids, Nielsens rules

Compounds which are highly colored are likely to contain a long-chain conjugated system (4~5) or a polycyclic aromatic chromophore.

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Homework and Course Requirements

Comprehend the rationale Ultraviolet and visible spectra t Master the fundamental type of electronic transition Master the major component parts and the demand of every part of visible ultraviolet spectrophotometer Finish Homework