Polyhedron 24 (2005) 2121–2125

www.elsevier.com/locate/poly

Synthesis, electrochemical and spectroscopic studies of

highly extended tetraaryl-m-phenylenediamines as precursors
of ground-state triplet dications
Masafumi Yano a,*, Teruyuki Furuya a, Masanori Yonezawa a, Masakazu Tatsumi a,
Munetaka Oyama b, Kazunobu Sato c, Takeji Takui c
a
Unit of Chemistry, Faculty of Engineering, Kansai University, Suita-shi, Osaka 564-8680, Japan
b
Division of Research Initiatives, International Innovation Center, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan
c
Department of Chemistry, Graduate School of Science, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan

Received 5 October 2004; accepted 8 December 2004

Available online 4 May 2005

Abstract

Two types of iodinated tetraaryl-1,3-phenylenediamine were designed and synthesized as useful building blocks for synthons in
organic syntheses. Various highly p-extended tetraaryl-1,3-phenylenediamines for charged high-spin molecular systems were suc-
cessfully synthesized from the precursors using Sonogashira coupling. Their electrochemical and spectroscopic properties were also
examined. The dications derived from highly p-extended tetraaryl-1,3-phenylenediamines were generated and characterized by elec-
tron transfer stopped-flow method. Some of the monocation radicals were short-lived.

2005 Elsevier Ltd. All rights reserved.

Keywords: Charged organic high-spin systems; Oligoarylamines; Sonogashira coupling; Electron transfer stopped-flow method; Cyclic voltammetry

1. Introduction ground-states. Actually, we previously reported that oli-

Over the last few decades, charged purely organic
high-spin systems have been the subject of controversy
[1,2]. Among them, several articles have been devoted
to the study of positively charged high-spin molecular
systems generated by hole doping, which have been
attracting much attention as models for studying an
interplay between pluricharge fluctuation and spin
polarization in p-electron networks. Oligoarylamines,
in which two or more nitrogen cores are meta-
connected, are promising precursors [2]. As the precur-
sors have topologically pseudo-degenerate HOMOs,
the corresponding oligocationic states formed upon plu-
ral electron removal are expected to exhibit high-spin
*
Corresponding author. Tel.: +81 6 6368 0751; fax: +81 6 6330 3770.
E-mail address: myano@ipcku.kansai-u.ac.jp (M. Yano).
gotriarylamines with two or three meta-connected dia-
rylamino groups (1, 2) (Fig. 1) exhibit a stable triplet
or quartet ground state upon multi-electron oxidation,
respectively [2b,2c]. Similar oligoarylamine-based deriv-
atives were also reported by other groups [2d,2e,2f,
2g,2h]. Purely organic high-spin systems have attracted
continuing attention in view of not only fundamental
interest but also potential applications to molecular de-
vices and supramolecular systems. Although generation
and characterization of exotic high-spin molecules have
been an important issues in spin chemistry and materials
science during the past decades, little attention has been
paid to their possibilities as ‘‘synthons’’ for organic
syntheses.
Indeed, it is interesting to examine the possibilities,
but it has been confronted with great difficulty due to
the instabilities of the high-spin molecules or their pre-

0277-5387/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2005.03.028
2122 M. Yano et al. / Polyhedron 24 (2005) 2121–2125

H3 CO OCH3 been utilized in many laboratories for syntheses of nat-

N ural and artificial molecules. In this study, we propose
H3 CO OCH3 H3 CO
N N N N
OCH3 OCH3 OCH3 OCH3
1 2
0 0
Fig. 1. Structures of N,N,N ,N -tetrakis(p-anisyl)-4,6-dimethyl-1,3-
phenylenediamine (1) and N,N,N 0 ,N 0 ,N00 ,N00 -hexakis(p-anisyl)-1,3,5-
phenylenetriamine (2).
cursors. For example, poly(aryl)carbenes of particular
p-electron networks, well known high-spin molecules, can
usually survive only at low temperature, and their pre-
cursors, polydiazo derivatives, are thermally and photo-
chemically unstable except several cases. On the other
hand, we have shown that the structural modification
of tetraphenyl-m-phenylenediamine by suitable sub-
stituents is quite effective in stabilizing the dicationic
states, which are stable even at ambient temperature
[2c,2j].
Those oligoarylamines described above have no func-
tional group available for further extension of their
p-electron network, preventing us from utilizing them
in organic syntheses. So, we attempted to design and
synthesize functionalized tetraaryl-m-phenylenediam-
ines. Generally, aryl halides are widely used as conve-
nient compounds in conventional and modern
organometallic syntheses. Until now, numerous organic
syntheses using aryl halides have been reported. Among
them, Sonogashira coupling [3] is an attractive and pow-
erful method for syntheses of acetylene bridged com-
pounds in excellent yields. In fact, the coupling has
OCH3 two types of iodinated tetraaryl-1,3-phenylenediamines
(3 and 4) as ‘‘synthons’’ for molecular devices and
supramolecular systems. Furthermore, using Sonogash-
ira coupling, the compounds can be transformed into
highly extended tetraaryl-m-phenylenediamines.
2. Results and discussion
2.1. Molecular designs and syntheses of target molecules
As target molecules, we chose N,N,N 0 ,N 0 -tetrakis(4-
iodophenyl)-4,6-dimethyl-1,3-phenylenediamine (3) and
N-(4-iodophenyl)-N,N 0 ,N 0 -tris(4-methylphenyl)-4,6-di-
methyl-1,3-phenylenediamine (4). In the compounds,
the reactive iodo groups are introduced at the para-posi-
tions of the peripheral aryl ring, and in the middle part
of the molecules, the 4,6-positions of the central aryl
ring are capped with methyl groups, which can enhance
the stabilities of the mono- and dicationic states of tetra-
aryl-m-phenylenediamines. The synthetic routes of 3 and
4 are shown in Fig. 2.
Synthesis of 3: 5-Nitro-2,4-xylidine was reduced with
tin dichloride/hydrochloric acid in ethanol to give 4,6-
dimethyl-1,3-phenylenediamine (5), which was reacted
with iodobenzene under Ullmann coupling condition [4]
to give N,N,N 0 ,N 0 -tetraphenyl-4,6-dimethyl-1,3-pheny-
lenediamine (6) (yield 56% for the two steps). This com-
pound was iodinated with potassium iodide/potassium
iodate in acetic acid to give 3, which was purified by col-
umn chromatography (CHCl3/n-hexane = 1/3) in 93%
isolated yield.

X X
SnCl2/ HCl I
N N
H2 N NO2 EtOH H2 N NH2 Cu/ K2CO3
5 18-crown-6
o-Dichlorobenzene
X X
6: X=H
KI/ KIO3/ AcOH
3: X=I

I SnCl2 / HCl
O2 N NH2 Cu/ K2CO3 O2 N N EtOH H2N N
18-crown-6 H H
o-Dichlorobenzene 7 8

I
I N N KI/ KIO3 N N
Cu/ K2CO3 AcOH
18-crown-6
o-Dichlorobenzene
9 4

Fig. 2. Synthetic routes for 3 and 4.

 M. Yano et al. / Polyhedron 24 (2005) 2121–2125
3: 1H NMR d 1.97 (s 6H), 6.65 (d, 8H, J = 8.91 Hz),
6.82 (s, 1H), 7.10 (s, 1H), 7.38 (d, 8H, J = 8.91 Hz).
Synthesis of 4: 5-Nitro-2,4-xylidine was reacted with
iodobenzene to give N-diphenyl-5-nitro-2,4-xylidine (7)
in 35% isolated yield. Stoichiometrically, only one
equivalent of iodobenzene is required to obtain 7, how-
ever, the best result was obtained when 5-nitro-2,4-xyli-
dine was reacted with iodobenzene in the ratio of 1:2
under reflux for 7 h. Prolonged reaction time gave the
undesired di-substituted compound, N,N-diphenyl-5-ni-
tro-2,4-xylidine, predominantly. The compound 7 was
quantitatively reduced with tin dichloride/hydrochloric
acid in ethanol to give N-phenyl-4,6-dimethyl-1,3-
phenylenediamine (8), which was reacted with an excess
amount of p-iodotoluene under Ullmann coupling reac-
tion to give N,N 0 ,N 0 -tris(4-methylphenyl)-N-phenyl-4,6-
dimethyl-1,3-phenylenediamine (9), in 49% isolated
yield. Compound 9 was iodinated with potassium
iodide/ potassium iodate in acetic acid to give 4, which
was purified by column chromatography (CHCl3/n-hex-
ane = 1/5) in quantitative yield.
4: 1H NMR d 1.97 (s, 3H), 1.99 (s, 3H), 2.25 (s, 6H),
2.31 (s, 3H), 6.62 (d, 2H, J = 8.90 Hz), 6.80 (d, 4H,
J = 8.40 Hz), 6.87 (d, 2H, J = 8.90 Hz), 6.89 (d, 2H,
J = 8.90 Hz), 6.90 (s, 1H), 7.00 (d, 4H, J = 8.40 Hz),
7.06 (s, 1H), 7.37 (d, 2H, J = 8.90 Hz).
2.2. p-Extension using Sonogashira coupling
In order to examine the reactivity of 3 and 4, various
acetylene compounds were coupled with them under
Sonogashira coupling condition [3a] to obtaine
p-extended tetraaryl-m-phenylenediamines (10a–e and
11a–d) shown in Fig. 3. The synthetic procedure of
10a is described below.
Compound 3 was mixed with a catalytic amount of
copper iodide, dichlorobis (triphenylphosphine) palla-
R R
R 10b; R= H
3 N N
CuI
Cl2Pd(PPh3 )2
NEt 3
R R
R
4 N N 11c; R=
CuI
Cl2Pd(PPh3 )2
NEt3
Fig. 3. Synthetic routes for 10a–e and 11a–d.
2123
dium (II) and six equivalents of trimethylsilylacetylene,
and stirred under argon atmosphere for 12 h at ambient
temperature. The obtained crude oil was purified by col-
umn chromatography (CHCl3/n-hexane = 1/1) in 98%
yield. Compounds 10c–e and 11a, c–d were also pre-
pared in a similar manner. Compounds 10b and 11b
were prepared by desilylation of 10a and 11a in the pres-
ence of potassium carbonate in methanol/THF in quan-
titative yield. The NMR spectra of these molecules are
consistent with their assigned structures.
2.3. UV/Vis spectroscopic and cyclic voltammetry
measurements
Compounds 3 exhibited a broad absorption band
around 300 nm in chloroform, which is characteristic
of triarylamine chromophores. Comparing with the
UV/Vis spectrum of 1, no significant difference was ob-
served between 1 and 3, indicating their similar electronic
structures. Also compound 4 exhibited a similar absorp-
tion band (kmax = 301 nm). Upon cyclic voltammetry in
n-butyronitrile with 0.1 M Bu4NPF6 as a supporting
electrolyte, Compounds 3 and 4 showed two sets of
reversible redox couples (3: E01 ¼ 679 mV; E02 ¼ 854 mV
versus Fc/Fc+, 4: E01 ¼ 428 mV; E02 ¼ 678 mV versus Fc/
Fc+), respectively. These results indicate that 3 and 4
yield the stable mono- and dications upon consecutive
oxidation.
The UV/Vis spectra of 10a–e in chloroform exhib-
ited a broad absorption maximum around 375 nm,
which are remarkably red-shifted in comparison with
that of 1. On the other hand, the UV/Vis spectra of
11a–d in chloroform exhibited an absorption maximum
around 300 nm. Besides the absorption peak, another
absorption was observed around 360 nm. The spectra
of 10e and 11d are shown in Fig. 4 as representative
cases. A preliminary study revealed that 10a–d and
10a; R= TMS
K 2CO 3/ CH3OH/ THF
10c; R= 10e; R=
10d; R= CH3
11a; R= TMS
R
11b; R= H
CH3
11d; R=
2124
4 TDBPA+/TDBPA couple is 1.06 V versus Fc/Fc+,
(b)
3 Compound 10a, upon mixing with one equivalent of
Absorbance
2
(a)
1 shifted by 131 nm, indicating the occurrence of effective
0 Similarly, mixing with two equivalent of TDBPA+,
250 350 450
Wavelength (nm)
Fig. 4. Absorption spectra of: (a) 10e, (b) 11d in chloroform.
11c–11d exhibit fluorescent emission upon irradiation
of ultraviolet light.
Compounds 10a showed well resolved two sets of
reversible redox couples (E01 ¼ 608 mV; E02 ¼ 753 mV
versus Fc/Fc+), however, compounds 10b showed the
first oxidation wave at 550 (versus Fc/Fc+), followed
by two oxidation peaks upon further sweeping, and no
reduction wave was observed, indicating that monoca-
tion radical 10b+ is unstable. Similarly, compounds
10c–e showed similar complicated voltammograms, sug-
gesting the generation of unstable monocation radicals.
Compound 11a showed two sets of reversible redox
couples (E01 ¼ 430 mV; E02 ¼ 660 mV versus Fc/Fc+),
while compound 11b showed the first reversible redox
couple and the second quasi-reversible redox couple
(E01 ¼ 434 mV; E02 ¼ 678 mV versus Fc/Fc+). Similarly,
compounds 11c–d gave stable monocation radical and
fairly unstable dication, respectively (11c: E01 ¼ 429 mV;
E02 ¼ 612 mV, 11d: E01 ¼ 430 mV; E02 ¼ 617 mV versus
Fc/Fc+).
2.4. Electron transfer stopped-flow method measurements
As a novel method to observe the absorption spectra
of short-lived cation radicals in solution, one of the
authors (M.O.) has proposed electron transfer
stopped-flow (ETSF) method [5,6]. Using this technique,
the absorption spectra of aromatic amine cation radicals
were successfully detected, and the kinetic processes
were analyzed. The ETSF measurements were carried
out in dehydrated acetonitrile (AN) as a solvent at ambi-
ent temperature. Depending on the oxidation potential
of each compound, tris(4-bromophenyl)amine cation
radical (TBPA+) or tris(2,4-dibromophenyl)amine cat-
ion radical (TDBPA+), more powerful oxidizing re-
agents, are employed.1 The formal potential of
1
TDBPA was synthesized by WAKO Pure Chemicals Ltd. after
receiving our special order. See also Ref. [5].
M. Yano et al. / Polyhedron 24 (2005) 2121–2125
which is 0.44 V positive to that of TBPA+/TBPA cou-
ple. In this study, TDBPA+ was employed.
TDBPA+, exhibited a broad absorption peak at 816 nm
(Fig. 5), and any significant decrease in the peak inten-
sity was not observed over 1 min. Compared with the
spectrum of 1+ [2j], the kmax of 10a+ is extremely red
p-network extension. The molar absorptivity (e) of 10a+
was determined to be 2.19 · 104 M
1 cm
1 at 816 nm.
550 10a showed an absorption peak at 842 nm
(e = 4.41 · 104 M
1 cm
1), which was slightly reduced
over 10 s.
On the other hand, upon mixing with one equivalent
of TDBPA+, compound 10b, TMS deprotected com-
pounds, exhibited a weak absorption peak at 710 nm
(e = 1.05 · 104 M
1 cm
1) (Fig. 5), any significant de-
crease in the peak intensity was not observed over
1 min. It seems that the peak is derived from monoca-
tion radical 10a+. No significant difference in electronic
structure between 10a+ and 10b+ would be expected.
However, compared with the spectrum of 10a+, kmax
of 10b upon one electron oxidation is much red shifted,
and the intensity of the peak at 710 nm is about one-
fourth of that of 10a+ at 816 nm. Moreover, no spec-
trum change was observed by changing the substrate/
oxidizing reagent concentration ratio. On the basis of
the results described above, we concluded that the life-
time of 10b+ is too short to be determined even by the
ETSF method, and that the species observed is not
10b+ but other stable species produced by follow-up
reactions. Decomposition process is not clear yet, but
an AM1 calculation suggested that both compounds
10a and 10b have large electron densities at the terminal
acetylene carbon atoms. Bulky trimethylsilyl substituent
in 10a would protect the site effectively, suppressing
50000
(b)
40000
(mol-1 cm-1)
30000
(a)
20000
10000
(c)
0
550 600 650 700 750 800 850
Wavelength (nm)
Fig. 5. Absorption spectra observed after mixing of an AN solution of
0.10 mM TDBPA+ with an AN solution of: (a) 0.10 mM of 10a;
(b) 0.05 mM of 10a; (c) 0.10 mM of 11a.
 M. Yano et al. / Polyhedron 24 (2005) 2121–2125
follow-up reactions. Similar to 10b, both compounds
10c and 10d gave very unstable monocation radicals.
The ETSF measurements for 11a–d are now underway.
As ETSF measurements revealed that 10a gives the
corresponding mono- and dicationic states, we tried to
carry out ESR measurements of the species. We selected
SbCl5 as an oxidant, which is widely used for electron
oxidation of various organic compounds. Upon addi-
tion of two equivalents of SbCl5 into a CH2Cl2 solution
of 10a, the color of the solution immediately turned
blue, however, followed by rapid discoloration to red
in less than a few seconds at ambient temperature.
Any dominant fine-structure spectra attributable to the
short-lived high-spin entities in solution could not be
identified at glassy solvents at low temperature: Only
trace from the short-lived triplet species or monocat-
ionic ones was detected by conventional continuous
wave ESR spectroscopy. This indicated the occurrence
of rapid follow-up reactions in solution at ambient tem-
perature. Surprisingly, addition of one equivalent of
SbCl5 gave a similar result. These results indicate that
both the mono- and dicationic states are very unstable
under the condition. Other oxidants such as cerium
ammonium nitrate (CAN)/AN were met with failure.
Resolution of these difficulties is the target of future
work, exploring alternative oxidants.
3. Summary
In conclusion, we have designed and successfully
synthesized iodinated tetraaryl-1,3-phenylenediamines
(3 and 4). In designing novel molecular devices and
supramolecular systems, these compounds will serve
as intriguing building blocks, which are expected to ex-
hibit triplet ground states upon two electron oxidation.
Starting from 3 and 4, highly p-extended tetraaryl-1,3-
phenylenediamines (10a–e, 11a–d) have been synthe-
sized in excellent yields by Sonogashira coupling. The
2125
ETSF measurements showed that only 10a gives the
stable dication, probably due to steric protection.
Unfortunately, 10b–e gave very short-lived monocation
radicals. We are currently exploring effective aryl
groups that can protect the acetylene site. Molecular
designs and syntheses of novel photochemically or elec-
trochemically active derivatives coupled with 3 or 4 are
also in progress.
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