Synthesis and chemical properties of diacetylenes with pyridinium and 4,4′-bipyridinium groups

Article abstract of DOI:10.1002/hlca.200900309

Diacetylenes (DAs) having a dipolar D-π-A structure (D = donor: amino group; π = π-conjugation core; A = acceptor: pyridinium (Py) and bipyridinium (BPy) groups), i.e., 4 (APBPyDA) and 5 (APPyPyDA), or an A-π-A structure, i.e., 7 (DBPyDA) and 8 (PyDA(Cl)), were obtained by 1 : 1 and 1 : 2 reactions of 4,4′-(buta-1,3-diyne-1,4-diyl)bis[benzenamine] (APDA; 3) with 1-(2,4-dinitrophenyl)-1′-hexyl-4,4′-bipyridinium bromide chloride (1 : 1 : 1) (1), 1-(2,4-dinitrophenyl)-4-(pyridin-4-yl)pyridinium chloride (2), or 1-(2,4-dinitrophenyl)pyridinium chloride (6) (Schemes 1 and 2). The anion-exchange reactions of 8 with NaI and Li(TCNQ) (TCNQ^-=2, 2′-(cyclohexa-2,5-diene-1,4-diylidene)bis[propanedinitrile] radical ion (1-)) yielded the corresponding I^- and TCNQ^- salts 9 (PyDA(I)) and 10 (PyDA(TCNQ)). Compounds 10 and 4 exhibited a UV/VIS absorption due to a charge transfer between the TCNQ^- and the pyridinium groups and a strong solute - solvent interaction of a dipolar solute molecule in the polar environment, respectively. Compounds 8-10 exhibited photoluminescence in solution, whereas 4 and 7 did not because of the presence of the 4,4′-bipyridinium quenching groups. Differential-scanning-calorimetry (DSC) measurements suggested that the DAs obtained in this study can be converted into poly(diacetylenes) by thermal polymerization.

Full text of DOI:10.1002/hlca.200900309

Helvetica Chimica Acta – Vol. 93 (2010)
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Synthesis and Chemical Properties of Diacetylenes with Pyridinium and
4,4’-Bipyridinium Groups
by Isao Yamaguchi*, Hideo Higashi, Shunsuke Kimura, and Moriyuki Sato
Department of Material Science, Faculty of Science and Engineering, Shimane University,
1060 Nishikawatsu, Matsue 690-8504, Japan (phone: þ 81-852-326421,
e-mail: iyamaguchi@riko.shimane-u.ac.jp)
Diacetylenes (DAs) having a dipolar D-p-A structure (D ¼ donor: amino group; p ¼ p-conjugation
core; A ¼ acceptor: pyridinium (Py) and bipyridinium (BPy) groups), i.e., 4 (APBPyDA) and 5
(APPyPyDA), or an A-p-A structure, i.e., 7 (DBPyDA) and 8 (PyDA(Cl)), were obtained by 1:1 and
1:2 reactions of 4,4’-(buta-1,3-diyne-1,4-diyl)bis[benzenamine] (APDA; 3) with 1-(2,4-dinitrophenyl)-
1’-hexyl-4,4’-bipyridinium bromide chloride (1:1:1) (1), 1-(2,4-dinitrophenyl)-4-(pyridin-4-yl)pyridini-
um chloride (2), or 1-(2,4-dinitrophenyl)pyridinium chloride (6) (Schemes 1 and 2). The anion-exchange
reactions of 8 with NaI and Li(TCNQ) (TCNQꢀ ¼ 2,2’-(cyclohexa-2,5-diene-1,4-diylidene)bis[propa-
nedinitrile] radical ion (1ꢀ)) yielded the corresponding Iꢀ and TCNQꢀ salts 9 (PyDA(I)) and 10
(PyDA(TCNQ)). Compounds 10 and 4 exhibited a UV/VIS absorption due to a charge transfer between
the TCNQꢀ and the pyridinium groups and a strong solute – solvent interaction of a dipolar solute
molecule in the polar environment, respectively. Compounds 8 – 10 exhibited photoluminescence in
solution, whereas 4 and 7 did not because of the presence of the 4,4’-bipyridinium quenching groups.
Differential-scanning-calorimetry (DSC) measurements suggested that the DAs obtained in this study
can be converted into poly(diacetylenes) by thermal polymerization.
Introduction. – Diacetylenes (DAs, i.e., butadiynes) are an important class of
compounds that can be converted into functional materials such as polydiacetylenes
(PDAs) for third-order nonlinear optical devices [1], thiophene derivatives for organic
light-emitting devices [2], and oligoenes/oligoynes for molecular wires [3]. Pyridinium
salts have attracted considerable attention because of their applications in cationic
surfactants [4], nonlinear optical materials [5], phase-transfer catalysts [6], and also as
initiators of cationic polymerization [7]. Similarly, 1,1’-disubstituted 4,4’-bipyridinium
salts (viologens) have attracted attention since these species have interesting redox
properties and are components of numerous supramolecular systems [8]. Therefore,
DAs having pyridinium and 4,4’-bipyridinium moieties are expected to be useful as
starting species for the development of new functional materials. Recently, it has been
reported that DAs having terminal pyridinium groups exhibit interesting optical
properties such as two-photon absorption (TPA); DAs having a dipolar D-p-A
structure (D ¼ donor, p ¼ p-conjugation core, A ¼ acceptor) have a large TPA cross-
section (s(2)) [9]. From these results, DAs having both 4,4’-bipyridinium and electron-
donating groups are expected to exhibit interesting optical properties. To the best of
our knowledge, however, there have been no reports on DAs having a 4,4’-bipyridinium
moiety.
ꢀ 2010 Verlag Helvetica Chimica Acta AG, Zꢁrich

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DAs are usually synthesized by the coupling of alk-1-ynes [10]. However, this
method is not suitable for the synthesis of D-p-A-type DAs because the cross-coupling
reaction of alk-1-ynes with D or A units not only yields the desired D-p-A-type DAs
but also homo-coupling D-p-D- and A-p-A-type products.
Recently, we reported two Zincke salts, i.e., 1 and 2, that can react with primary
amines to yield various pyridinium and bipyridinium salts [11]. These salts can be useful
materials for the synthesis of D-p-A-type DAs. In this work, 4,4’-(buta-1,3-diyne-1,4-
diyl)bis[benzenamine] (APDA; 3) was used as building block for the synthesis of DAs
with pyridinium and 4,4’-bipyridinium moieties; the 1:1 and 2 :1 reactions of 1 and 2
with 3 yielded D-p-A and A-p-A type DAs (D ¼ NH2, A ¼ pyridinium or bipyridi-
nium), respectively. Herein, we report the synthesis and the optical, electrochemical,
and thermal properties of DAs having pyridinium, bipyridinium, and amino groups.
Results and Discussion. – The reactions of bis[benzenamine] 3 with 1-(2,4-
dinitrophenyl)-1’-hexyl-4,4’-bipyridinium bromide chloride (1:1:1) (1) and 1-(2,4-
dinitrophenyl)-4-(pyridin-4-yl)pyridinium chloride (2) in a 1:1 molar ratio afforded D-
p-A-type 4 (APBPyDA) and 5 (APPyPyDA) in 60% and 66% yield, respectively
(Scheme 1). The reaction of 3 with 1 or 1-(2,4-dinitrophenyl)pyridinium chloride (6) in
a 1:2 molar ratio afforded 7 (DBPyDA) or 8 (PyDA(Cl)) in 60% and 42% yield,
respectively (Scheme 2). It has been reported that the chemical properties and
polymerization behavior of DAs with pyridinium rings depend on their counter anions
[12]. Among the counter anions, TCNQꢀ (radical anion) can form pyridinium salts that
exhibit unique optical and electrical properties (TCNQ ¼ 2,2’-(cyclohexa-2,5-diene-1,4-
diylidene)bis[propanedinitrile]) [13]. Therefore, anion-exchange reactions were
carried out with 8; its reaction with an excess of NaI and with Li(TCNQ) yielded 9
(PyDA(I)) and 10 (PyDA(TCNQ)) in 54% and 85% yield, respectively (Scheme 2).
The complete anion exchanges were confirmed by elemental analysis.
1
The structures of the DAs obtained in this study were determined by H- and
13C-NMR spectra and elemental analysis. Fig. 1 shows the 1H-NMR spectra of 3, 7, and
4 in (D6)DMSO with the signal assignments. The phenylene H-atoms of 7 (DBPyDA)
appear as a s at d 8.05. This observation suggests that the bipyridinium and diacetylene
groups of 7 have similar electron-withdrawing properties. The signal at d 5.91 in the
1H-NMR spectrum of 4 (APBPyDA) can be assigned to the H-atoms of NH2; this
assignment is supported by the fact that the signal vanishes on addition of D2O to the
sample. Fig. 2 shows the 1H-NMR spectra of 8 – 10 in (D6)DMSO. A signal due to the
pyridinium H-atoms Hc in the spectra of 8 (PyDA(Cl)), 9 (PyDA(I)), and 10
(PyDA(TCNQ)) shifts to a higher magnetic field with an increase in the size of the
counter anion. However, the chemical shifts of the other signals are independent of the
type of counter anions. The presence of a radical anion in TCNQꢀ causes the
1
disappearance of its own H-NMR signal and the appearance of the low-resolution

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Scheme 1. Synthesis of D-p-A-Type DAs
821
Scheme 2. Synthesis of A-p-A-Type DAs and Their Anion-Exchange Reactions
1H-NMR signals due to the pyridinium and phenylene H-atoms of 10. The integrals of
the signals support the structures of the above DAs.
The 13C-NMR spectra of the symmetrical compounds 7 – 10 exhibited two signals at
d ca. 81 and 75 due to the butadiyne group. In the 13C-NMR spectra of the asymmetrical
compounds 4 and 5, four signals which are assignable to the butadiyne group appeared
at d ca. 87, 79, 78, and 71.
Fig. 3 shows the IR spectra of 8 (PyDA(Cl)), 10 (PyDA(TCNQ)), 7 (DBPyDA),
and 4 (APBPyDA). The bands due to n˜(CꢁC) of 8, 10, 7, and 4 depend on the
structures of the DAs; 7 and 8 have a symmetrical structure, and they exhibit a weak

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Fig. 1. 1H-NMR Spectra of 3 (APDA), 7 (DBPyDA), and 4 (APBPyDA) in (D6)DMSO
absorption for n˜(CꢁC) at ca. 2200 cmꢀ1. This observation corresponds to a small dipole
moment in the butadiyne moiety of the DAs having a symmetrical structure. In the IR
spectrum of 10, the absorption for n˜(CꢁC) overlaps with the strong absorption for
n˜(CꢁN) of TCNQꢀ at 2173 cmꢀ1. In contrast, 4 has an asymmetrical structure, and it
exhibits two absorptions at 2160 and 2200 cmꢀ1 from the symmetric and asymmetric
stretching vibrations of the CꢁC bonds, respectively. This observation is consistent with
the fact that the IR spectra of asymmetrical diacetylenes exhibit two absorptions for
n˜(CꢁC), as reported previously [14].
The optical data of the DAs obtained in this study are summarized in the Table. The
UV/VIS spectrum of 8 (PyDA(Cl)) in MeOH exhibits absorptions at ca. 250 and
325 nm (Fig. 4). In addition to these absorptions, 10 (PyDA(TCNQ)) in MeOH shows

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Fig. 2. 1H-NMR Spectra of 8 (PyDA(Cl)), 9 (PyDA(I)), and 10 (PyDA(TCNQ)) in (D6)DMSO
absorptions due to the charge-transfer (CT) bands between TCNQꢀ and the
pyridinium moiety in the range of 420 – 838 nm. These wavelengths are similar to
those of pyridinium TCNQꢀ salts reported previously [13]. The UV/VIS spectrum of 7
(DBPyDA) displays absorptions at longer wavelengths as compared to 8 (PyDA(Cl))
and 4 (APBPyDA) because of the longer p-conjugation system of 7. However, 4
exhibits a broader band at 328 with an onset position at ca. 550 nm. This band is
attributed to the strong solute – solvent interaction in the dipolar solute molecule in a
polar environment. It has been reported that a dipolar D-p-A-type butadiyne exhibits a
broader absorption than a quadrupolar A-p-A-type butadiyne [9].

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Fig. 3. IR Spectra of 8 (PyDA(Cl)), 10 (PyDA(TCNQ)), 7 (DBPyDA), and 4 (APBPyDA)
The DAs 8 – 10 were photoluminescent in MeOH, with the wavelengths of the
photoluminescence being independent of the counter anions (see Table). The DAs 7
and 4 were not photoluminescent, which is consistent with the fact that viologens
induce a quenching effect on the photoluminescence of aromatic compounds.
Differential-scanning-calorimetry (DSC) measurements are useful to obtain
information on the possibility of thermal polymerization of DAs; the heat (DH) of

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Table. Optical and Thermal Properties of DAs
825
Absorption [nm]a)
PL
[nm]b)
Texo [8]c) DH
[kcal/mol]d)
4
5
7
8
9
(APBPyDA)
(APPyPyDA)
(DBPyDA)
(PyDA(Cl))
(PyDA(I))
268 (4.38), 328 (4.40)
255 (4.49), 323 (4.40)
271 (4.56), 355 (4.42)
249 (4.79), 324 (4.83)
222 (4.72), 325 (4.49)
230
228
263
340
310
240
32
29
16
23
15
17
480
479
10 (PyDA(TCNQ)) 290 (4.72), 325 (4.46), 422 (4.45), 687 (4.04), 481
751 (4.55), 768 (4.51), 832 (4.59), 851 (4.73)
a) In MeOH; log e in parentheses. b) Photoluminescence (PL) in MeOH. c) Temperature at which an
exothermic peak was observed. d) Heat of polymerization estimated from the integral of the exothermic
peak.
Fig. 4. UV/VIS Spectra of 8 (PyDA(Cl)), 10 (PyDA(TCNQ)), 7 (DBPyDA), and 4 (APBPyDA) in
MeOH
1,4-addition polymerization of DAs that can be estimated from the integral of an
exothermic peak is in the range of 30 – 37 kcal/mol [15]. The DSC curves of 8
(PyDA(Cl)) and 7 (DBPyDA) exhibited an exothermic peak at 3408 and 2638,
respectively; at this point, the heats of polymerization (DH) were estimated to be 23
and 16 kcal/mol, respectively (see Table). These DH values are comparable to those of
the conventional 1,4-addition polymerization of DAs [15], suggesting that 7 and 8 can
be converted into 1,4-addition poly(diacetylenes) by thermal polymerization. The
Table summarizes the temperatures at which the exothermic peak of 9 (PyDA(I)), 10
(PyDA(TCNQ)), and 4 (APBPyDA) was observed and the DH values estimated from
the integral of the exothermic peak. In the series of DAs 8 – 10 with pyridinium rings,

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the temperature at which the exothermic peak was observed decreased with the size of
the counter anion. This behavior is in agreement with the assumption that the bulky
counter anions prevent the packing of the DA molecules that can easily cause thermal
polymerization.
The results demonstrate that new DAs can be obtained by reaction of Zincke salts
with 4,4’-(buta-1,3-diyne-1,4-diyl)bis[benzenamine] (3), and that the thermal polymer-
ization of DAs may provide new functional materials.
Experimental Part
General. Solvents were dried, distilled, and stored under N2. The 1-(2,4-dinitrophenyl)pyridinium
chloride (1:1) (6) [16], 1-(2,4-dinitrophenyl)-1’-hexyl-4,4’-bipyridinium bromide chloride (1:l :1) (1)
[11a], 1-(2,4-dinitrophenyl)-4-(pyridin-4-yl)pyridinium chloride (¼1-(2,4-dinitrophenyl)-4,4’-bipyridini-
um chloride (1:1); (2) [11b], and Li(TCNQ) [17] were prepared according to the literature. Other
reagents were purchased and used without further purification. Reactions were carried out with standard
Schlenk techniques under N2. DSC Measurements: Shimadzu-DSC-50 instrument.
UV/VIS Spectra: Jasco-V-560 spectrometer. Photoluminescence: Jasco-FP-6200 spectrometer. IR
Spectra: Jasco-FT/IR-660-Plus spectrophotometer. NMR Spectra: Jeol-AL-400 spectrometer; d in ppm,
J in Hz. Elemental analyses: Yanagimoto-MT-5 CHN analyzer.
4,4’-(Buta-1,3-diyne-1,4-diyl)bis[benzenamide] (3; APDA). Cu(OAc)2 (0.91 g, 5.0 mmol) was added
to a soln. of 4-ethynylbenzenamine (0.23 g, 2.0 mmol) in pyridine/MeOH 1:1 (v/v; 20 ml). After the soln.
was stirred at 208 for 24 h, the solvents were evaporated, and the resulting solid was extracted with
acetone. The acetone was evaporated and the resulting solid washed with H2O and dried in vacuo: 3
(0.21 g, 99%). Brown powder. 1H-NMR (400 MHz, (D6)DMSO; cf. Fig. 1): 7.18 (d, J ¼ 8.4, 4 H); 6.50 (d,
J ¼ 8.4, 4 H): 5.69 (br., 4 H). 13C-NMR (100 MHz, (D6)DMSO): 150.1; 133.5; 113.5; 106.4; 82.9; 72.0.
Anal. calc. for C16H12N2: C 82.73, H 5.21, N 12.06; found: C 82.60, H 5.41, N 12.29.
1,1’’-(Buta-1,3-diyne-1,4-diyldi-4,1-phenylene)bis[1’-hexyl-4,4’-bipyridinium] Bromide Chloride
(1:2 :2) (7; DBPyDA). Bis[benzamine] 3 (0.23 g, 1.0 mmol) and 1 (1.6 g, 3.0 mmol) were dissolved in
DMSO (15 ml) at 908. After the mixture was stirred at 908 for 24 h, the solvent was evaporated and the
resulting solid washed with acetone and extracted with hot H2O (ca. 958). After evaporation of the H2O,
the resulting solid was washed with MeOH (5 ml) and dried in vacuo: 7 · H2O (0.54 g, 60%). Yellow
powder. 1H-NMR (400 MHz, (D6)DMSO; cf. Fig. 1): 9.69 (d, J ¼ 6.4, 4 H); 9.45 (d, J ¼ 6.4, 4 H); 8.99 (d,
J ¼ 6.8, 4 H); 8.93 (d, J ¼ 6.4, 4 H); 8.05 (s, 8 H); 4.69 (t, J ¼ 7.2, 4 H); 1.96 (t, J ¼ 6.4, 4 H); 1.28 (s, 12 H);
0.84 (t, J ¼ 7.2, 6 H). 13C-NMR (100 MHz, (D6)DMSO): 149.6; 148.0; 145.90; 145.87; 142.7; 134.3; 126.8;
126.5; 125.8; 123.4; 81.4; 75.6; 60.9; 30.8; 30.6; 25.1; 21.9; 13.9. Anal. calc. for C48H50Br2Cl2N4 · H2O: C
61.88, H 5.63, N 6.01; found: C 62.01, H 5.70, N 5.89.
1-{4-[4-(4-Aminophenyl)buta-1,3-diyn-1-yl]phenyl}-1’-hexyl-4,4’-bipyridinium Bromide Chloride
(1:1:1) (4; APBPyDA). Bis[benzenamine] 3 (0.35 g, 1.5 mmol) and salt 1 (0.39 g, 0.75 mmol) were
dissolved in DMSO (22 ml). After the mixture was stirred at 908 for 24 h, the solvent was evaporated and
the resulting solid washed with acetone and extracted with hot H2O (ca. 958). The solvent was evaporated
1
and the resulting solid dried in vacuo: 4 · 0.4 H2O (0.54 g, 60%). Brown powder. H-NMR (400 MHz,
(D6)DMSO; cf. Fig. 1): 9.69 (d, J ¼ 6.4, 2 H); 9.45 (d, J ¼ 6.0, 2 H); 8.97 (d, J ¼ 6.4, 2 H); 8.93 (d, J ¼ 6.4,
2 H); 8.01 (d, J ¼ 8.4, 2 H); 7.97 (d, J ¼ 8.4, 2 H); 7.27 (d, J ¼ 8.8, 2 H); 6.56 (d, J ¼ 8.8, 2 H); 5.91 (s, 2 H);
4.72 (t, J ¼ 7.2, 2 H); 1.99 (br. s, 2 H); 1.31 (s, 6 H); 0.88 (t, J ¼ 6.4, 3 H). 13C-NMR (100 MHz,
(D6)DMSO): 151.1; 149.4; 148.0; 145.9; 145.7; 141.9; 134.1; 133.6; 126.8; 126.5; 125.5; 124.6; 113.6; 104.7;
86.5; 79.1; 77.7; 71.0; 60.8; 30.8; 30.6; 25.1; 21.9; 13.8. Anal. calc. for C32H31BrClN3 · 0.4 H2O: C 66.25, H
5.52, N 7.24; found: C 66.27, H 5.70, N 7.11.
1-{4-[4-(4-Aminophenyl)buta-1,3-diyn-1-yl]phenyl}-4,4’-bipyridinium Chloride (1:1) (5; APPyPy-
DA). As described for 4, with 3 and 2: 5 · 0.5 H2O (66%). 1H-NMR (400 MHz, (D6)DMSO): 9.51 (d, J ¼
6.4, 2 H); 8.91 (d, J ¼ 5.2, 2 H); 8.81 (d, J ¼ 6.4, 2 H); 8.16 (d, J ¼ 5.2, 2 H); 7.98 (d, J ¼ 8.8, 2 H); 7.94 (d,
J ¼ 8.4, 2 H); 7.27 (d, J ¼ 8.4, 2 H); 6.56 (d, J ¼ 8.0, 2 H); 5.91 (s, 2 H). 13C-NMR (100 MHz, (D6)DMSO):

Helvetica Chimica Acta – Vol. 93 (2010)
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151.0; 149.4; 147.9; 145.9; 145.6; 142.0; 134.1; 133.0; 126.7; 126.5; 124.9; 111.9; 104.0; 86.9; 79.0; 77.5; 70.8.
Anal. calc. for C26H18ClN3 · 0.5 H2O: C 74.90, H 4.59, N 10.08; found: C 75.05, H 4.70, N 10.37.
1,1’-(Buta-1,3-diyne-1,4-diyldi-4,1-phenylene)bis[pyridinium] Chloride (1:2) (8; PyDA(Cl)). Bis-
[benzenamine] 3 (0.75 g, 3.2 mmol) and 6 (2.7 g, 9.6 mol) were dissolved in DMSO (9 ml) and stirred at
908 for 48 h. The solvent was evaporated and the resulting solid extracted with H2O. The solvent was
evaporated and the resulting solid washed with acetone and dried in vacuo: 8 (0.57 g, 42%). Brown
powder. 1H-NMR (400 MHz, (D6)DMSO; cf. Fig. 2): 9.38 (d, J ¼ 5.6, 4 H); 8.81 (t, J ¼ 8.0, 2 H); 8.34 (t,
J ¼ 7.2, 4 H); 8.03 (d, J ¼ 8.8, 4 H); 7.98 (d, J ¼ 8.8, 4 H). 13C-NMR (100 MHz, D2O): 147.6; 144.9; 143.5;
135.1; 129.0; 125.2; 125.1; 81.3; 76.3. Anal. calc. for C26H18Cl2N2: C 72.73, H 4.23, N 6.52; found: C 72.59,
H 4.11, N 6.37.
1,1’-(Buta-1,3-diyne-1,4-diyldi-4,1-phenylene)bis[pyridinium] Iodide (1:2) (9; PyDA(I)). An aq.
soln. (5 ml) of NaI (1.8 g, 1.2 mmol) was added dropwise to an aq. soln. (5 ml) of 8 (0.093 g, 0.30 mmol).
After 6 h stirring at 208, the solvent was evaporated and the resulting solid washed with acetone and dried
under vacuum: 9 (0.10 g, 54%). Light brown powder. 1H-NMR (400 MHz, (D6)DMSO; cf. Fig. 2): 9.36
(d, J ¼ 5.6, 4 H); 8.81 (t, J ¼ 8.0, 2 H); 8.34 (t, J ¼ 7.2, 4 H); 8.03 (d, J ¼ 8.8, 4 H); 7.98 (d, J ¼ 8.8, 4 H).
13C-NMR (100 MHz, D2O): 147.4; 144.6; 143.3; 135.1; 128.9; 125.0; 125.0; 81.3; 76.3. Anal. calc. for
C26H18I2N2: C 51.01, H 2.96, N 4.58; found: C 50.54, H 2.99, N 3.77.
1,1’-(Buta-1,3-diyne-1,4-diyldi-4,1-phenylene)bis[pyridinium] 2,2’-(Cyclohexa-2,5-diene-1,4-diylide-
ne)bis[propanedinitrile] Radical Ion (1ꢀ) (1 :1) (10; PyDA(TCNQ)). An aq. soln. (5 ml) of Li(TCNQ)
(0.52 g, 2.4 mmol) was added dropwise to an aq. soln. (5 ml) of 9 (0.11 g, 0.18 mmol). After the mixture
was stirred at 208 for 6 h, the precipitate was collected from the mixture by filtration, washed with
1
acetone, and dried in vacuo: 10 · 0.1 H2O (0.096 g, 85%). Bluish purple powder. H-NMR (400 MHz,
(D6)DMSO; cf. Fig. 2): 9.35 (d, J ¼ 4.4, 4 H); 8.81 (2 H); 8.33 (4 H); 8.03 (4 H); 7.98 (4 H). 13C-NMR
(100 MHz, (D6)DMSO): 147.1; 145.1; 143.3; 134.4; 128.2; 125.7; 122.9; 81.2; 75.1. Anal. calc. for
C50H26N10 · 0.1 H2O: C 78.13, H 3.44, N 18.22; found: C 78.19, H 3.39, N 18.40.
REFERENCES
[1] A. Sarkar, S. Okada. H. Matsuzawa, H. Matsuda, H. Nakanishi, J. Mater. Chem. 2000, 10, 819.
[2] F. Morisaki, M. Kurono, K. Hirai, H. Tomioka, Org. Biomol. Chem. 2005, 3, 431; T. Itoh, F. Morisaki,
K. Hirai, H. Tomioka, J. Org. Chem. 2004, 69, 5870.
[3] Y. Asai, S. Hirata, K. Yamashita, J. Phys. Soc. Jpn. 2003, 72, 3286; S. Spagnoli, K. J. Donovan, K.
Scott, M. Somerton, E. G. Wilson, Chem. Phys. 1999, 250, 71; K. J. Donovan, E. G. Wilson, Synth.
Met. 1989, 28, D569.
[4] N. O. Mchedlov-Petrossyan, N. A. Vodolazkaya, A. A. Kornienko, E. L. Karyakina, C. Reichardt,
´
Langmuir 2005, 21, 7090; J. Pernak, J. Kalewska, H. Ksycinska, J. Cybulski, Eur. J. Med. Chem. 2001,
36, 899.
[5] H. Umezawa, S. Okada, H. Oikawa, H. Matsuda, H. Nakanishi, Bull. Chem. Soc. Jpn. 2005, 78, 344;
B. J. Coe, J. A. Harris, I. Asselberghs, K. Clays, G. Olbrechts, A. Persoons, J. T. Hupp, R. C. Johnson,
S. J. Coles, M. B. Hursthouse, K. Nakatani, Adv. Funct. Mater. 2002, 12, 110.
[6] D. Wang, M. Wang, X. Wang, R. Zhang, J. Ma, L. Sun, J. Mol. Catal. A: Chem. 2007, 270, 278; R. T.
Dere, R. R. Pal, P. S. Patil, M. M. Salunkhe, Tetrahedron Lett. 2003, 44, 5351.
[7] E. Takahashi, F. Sanda, T. Endo, J. Polym. Sci., Part A: Polym. Chem. 2002, 40, 1037; M. Onciu, A.
Onen, Y. Yagci, Polym. Int. 2001, 50, 144; W. Schnabel, Macromol. Rapid Commun. 2000, 628.
[8] J. Zhang, R. M. Lahtinen, K. Kontturi, P. R. Unwin, D. J. Schiffrin, Chem. Commun. 2001, 1818; S.
Yasui, K. Itoh, A. Ohno, N. Tokitoh, Chem. Lett. 2001, 1056; X. Zhao, X.-K. Jiang, M. Shi, Y.-H. Yu,
W. Xia, Z.-T. Li, J. Org. Chem. 2001, 66, 7035.
[9] K. Kamada, Y. Iwase, K. Sakai, K. Kondo, K. Ohta, J. Phys. Chem. C 2009, 113, 11469.
[10] P. Siemsen, R. C. Livingston, F. Diederich, Angew. Chem., Int. Ed. 2000, 39, 2632.
[11] a) I. Yamaguchi, N. Mizoguchi, M. Sato, Macromolecules 2009, 42, 4416; b) I. Yamaguchi, H.
Higashi, S. Shigesue, S. Shingai, M. Sato, Tetrahedron Lett. 2007, 48, 7778.

828
Helvetica Chimica Acta – Vol. 93 (2010)
[12] K. Shiga, T. Inoguchi, K. Mori, K. Kondo, K. Kamada, K. Tawa, K. Ohta, T. Maruo, E. Mochizuki, Y.
Kai, Macromol. Chem. Phys. 2001, 202, 257.
[13] G. Kobmehl, D. Kabbeck-Kupijal, S. N. Magonov, Synth. Met. 1991, 42, 2565.
[14] J. Y. Chang, J. R. Yeon, Y. S. Shin, M. J. Han, S.-K. Hong, Chem. Mater. 2000, 12, 1076.
[15] G. N. Patel, R. R. Chance, E. A. Turi, Y. P. Khanna, J. Am. Chem. Soc. 1978, 100, 6644.
[16] T. Zincke, G. Heuser, W. Mçller, Justus Liebigs Ann. Chem. 1904, 333, 296.
[17] L. R. Melby, R. J. Harder, W. R. Hertler, W. Mahler, R. E. Benson, W. E. Mochel, J. Am. Chem. Soc.
1962, 84, 3374.
Received August 28, 2009