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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
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
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
3: 1H NMR d 1.97 (s 6H), 6.65 (d, 8H, J = 8.91 Hz), dium (II) and six equivalents of trimethylsilylacetylene,
6.82 (s, 1H), 7.10 (s, 1H), 7.38 (d, 8H, J = 8.91 Hz). and stirred under argon atmosphere for 12 h at ambient
Synthesis of 4: 5-Nitro-2,4-xylidine was reacted with temperature. The obtained crude oil was purified by col-
iodobenzene to give N-diphenyl-5-nitro-2,4-xylidine (7) umn chromatography (CHCl3/n-hexane = 1/1) in 98%
in 35% isolated yield. Stoichiometrically, only one yield. Compounds 10c–e and 11a, c–d were also pre-
equivalent of iodobenzene is required to obtain 7, how- pared in a similar manner. Compounds 10b and 11b
ever, the best result was obtained when 5-nitro-2,4-xyli- were prepared by desilylation of 10a and 11a in the pres-
dine was reacted with iodobenzene in the ratio of 1:2 ence of potassium carbonate in methanol/THF in quan-
under reflux for 7 h. Prolonged reaction time gave the titative yield. The NMR spectra of these molecules are
undesired di-substituted compound, N,N-diphenyl-5-ni- consistent with their assigned structures.
tro-2,4-xylidine, predominantly. The compound 7 was
quantitatively reduced with tin dichloride/hydrochloric 2.3. UV/Vis spectroscopic and cyclic voltammetry
acid in ethanol to give N-phenyl-4,6-dimethyl-1,3- measurements
phenylenediamine (8), which was reacted with an excess
amount of p-iodotoluene under Ullmann coupling reac- Compounds 3 exhibited a broad absorption band
tion to give N,N 0 ,N 0 -tris(4-methylphenyl)-N-phenyl-4,6- around 300 nm in chloroform, which is characteristic
dimethyl-1,3-phenylenediamine (9), in 49% isolated of triarylamine chromophores. Comparing with the
yield. Compound 9 was iodinated with potassium UV/Vis spectrum of 1, no significant difference was ob-
iodide/ potassium iodate in acetic acid to give 4, which served between 1 and 3, indicating their similar electronic
was purified by column chromatography (CHCl3/n-hex- structures. Also compound 4 exhibited a similar absorp-
ane = 1/5) in quantitative yield. tion band (kmax = 301 nm). Upon cyclic voltammetry in
4: 1H NMR d 1.97 (s, 3H), 1.99 (s, 3H), 2.25 (s, 6H), n-butyronitrile with 0.1 M Bu4NPF6 as a supporting
2.31 (s, 3H), 6.62 (d, 2H, J = 8.90 Hz), 6.80 (d, 4H, electrolyte, Compounds 3 and 4 showed two sets of
J = 8.40 Hz), 6.87 (d, 2H, J = 8.90 Hz), 6.89 (d, 2H, reversible redox couples (3: E01 ¼ 679 mV; E02 ¼ 854 mV
J = 8.90 Hz), 6.90 (s, 1H), 7.00 (d, 4H, J = 8.40 Hz), versus Fc/Fc+, 4: E01 ¼ 428 mV; E02 ¼ 678 mV versus Fc/
7.06 (s, 1H), 7.37 (d, 2H, J = 8.90 Hz). Fc+), respectively. These results indicate that 3 and 4
yield the stable mono- and dications upon consecutive
2.2. p-Extension using Sonogashira coupling oxidation.
The UV/Vis spectra of 10a–e in chloroform exhib-
In order to examine the reactivity of 3 and 4, various ited a broad absorption maximum around 375 nm,
acetylene compounds were coupled with them under which are remarkably red-shifted in comparison with
Sonogashira coupling condition [3a] to obtaine that of 1. On the other hand, the UV/Vis spectra of
p-extended tetraaryl-m-phenylenediamines (10a–e and 11a–d in chloroform exhibited an absorption maximum
11a–d) shown in Fig. 3. The synthetic procedure of around 300 nm. Besides the absorption peak, another
10a is described below. absorption was observed around 360 nm. The spectra
Compound 3 was mixed with a catalytic amount of of 10e and 11d are shown in Fig. 4 as representative
copper iodide, dichlorobis (triphenylphosphine) palla- cases. A preliminary study revealed that 10a–d and
R R
10a; R= TMS
K 2CO 3/ CH3OH/ THF
R 10b; R= H
3 N N
CuI
Cl2Pd(PPh3 )2 10c; R= 10e; R=
NEt 3
10d; R= CH3
R R
11a; R= TMS
R
11b; R= H
R
4 N N 11c; R= CH3
CuI
Cl2Pd(PPh3 )2
NEt3 11d; R=
follow-up reactions. Similar to 10b, both compounds ETSF measurements showed that only 10a gives the
10c and 10d gave very unstable monocation radicals. stable dication, probably due to steric protection.
The ETSF measurements for 11a–d are now underway. Unfortunately, 10b–e gave very short-lived monocation
As ETSF measurements revealed that 10a gives the radicals. We are currently exploring effective aryl
corresponding mono- and dicationic states, we tried to groups that can protect the acetylene site. Molecular
carry out ESR measurements of the species. We selected designs and syntheses of novel photochemically or elec-
SbCl5 as an oxidant, which is widely used for electron trochemically active derivatives coupled with 3 or 4 are
oxidation of various organic compounds. Upon addi- also in progress.
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 References
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