Nanosized starlike molecules. Synthesis and optical properties of 2,4,6-tris(disilanylenebithienylene)-1,3,5-triazine derivatives

Article abstract of DOI:10.1016/j.jorganchem.2011.12.029

Starlike molecules (5) and (7) that have a triazine unit as a core and arms consisting of an alterative arrangement of an Si-Si bond and bithienylene unit were prepared by the Pd-catalyzed reactions of 2,4,6-tris[5-(1,3-dioxa-4,4,5,5- tetramethyl-2-borolanyl)-2-thienyl]triazine with 5- bromothienylpentamethyldisilane and with 1-(5-bromothienyl)-2- bithienyltetramethyldisilane, respectively. In the UV-vis absorption and fluorescence spectra, 5 and 7 showed absorption maxima in a range of 398-399 nm, and revealed higher fluorescence quantum yields than that of 2,4,6-tris(bithienyl)triazine.

Full text of DOI:10.1016/j.jorganchem.2011.12.029

Journal of Organometallic Chemistry 702 (2012) 67e72
Contents lists available at SciVerse ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Nanosized starlike molecules. Synthesis and optical properties of 2,4,
6
-tris(disilanylenebithienylene)-1,3,5-triazine derivatives
a
,
a
a
a
b
*
Akinobu Naka , Ryuichi Fukuda , Risa Kishimoto , Yukiko Yamashita , Yousuke Ooyama ,
b
a,
*
Joji Ohshita , Mitsuo Ishikawa
Department of Life Science, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajima-cho, Kurashiki, Okayama 712-8505, Japan
Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan
a
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 19 October 2011
Received in revised form
Starlike molecules (5) and (7) that have a triazine unit as a core and arms consisting of an alterative
arrangement of an SieSi bond and bithienylene unit were prepared by the Pd-catalyzed reactions of 2,4,6-tris
[
5-(1,3-dioxa-4,4,5,5-tetramethyl-2-borolanyl)-2-thienyl]triazine with 5-bromothienylpentamethyldisilane
17 December 2011
and with 1-(5-bromothienyl)-2-bithienyltetramethyldisilane, respectively. In the UVevis absorption and
fluorescence spectra, 5 and 7 showed absorption maxima in a range of 398e399 nm, and revealed higher
fluorescence quantum yields than that of 2,4,6-tris(bithienyl)triazine.
Accepted 26 December 2011
Keywords:
Ó 2011 Elsevier B.V. All rights reserved.
Starlike molecules
Disilanylenebithienylene
Triazine
UV absorption
Photoluminescence
1. Introduction
1,3,5-tris- and 1,2,4,5-tetrakis(silyl)benzene as a core and
bithienyleneedisilanylene units in the arms [5]. We have found
that the starlike molecules show novel optical properties, such as
high fluorescence quantum yields and long lifetimes of the excited
state. We have also found that these molecules can be used as the
functional device materials, such as optical recording materials [6]
and semiconductors in field-effect transistors [7].
It has been reported that 1,3,5-triazine compounds show good
optical and electrochemical properties, due to their electron
deficiency [8]. We considered that the starlike molecules
bearing triazine ring system as a core would show interesting
optical behavior. In this paper, we report the synthesis and
optical properties of the starlike molecules with a 1,3,5-triazine
unit as a core and three arms consisting of a regular alter-
nating arrangement of a siliconesilicon bond and a bithienylene
group.
The nanosized starlike molecules bearing arms that extend to
three directions have attracted much attention, because they show
interesting behavior due to their unique molecular structures.
Several types of the starlike molecules with conjugated p-electron
systems in their arms have been prepared and their optical prop-
erties have been investigated so far [1]. However, little interest has
been shown in the chemistry of the nanosized starlike molecules
with the arms that have an alternating arrangement of an SieSi
bond and a
p-electron unit, which extend to three directions,
although Ponomarenko and his coworkers have reported the
synthesis and optical properties of compounds including both
silylene and bithienylene units in the arms [2].
We have reported the synthesis and optical properties of several
types of the nanosized starlike molecules: the molecules bearing
a methyltris(silyl)silane unit as a core and the arms consisting of
a regular alternating arrangement of an SieSi bond and bithieny-
lene unit [3], the starlike molecules with the same core and oli-
gothienylene units as the arms [4], and the molecules including
2. Results and discussion
The method used for the synthesis of the present starlike
compounds bearing a 1,3,5-triazine unit as a core and an alternative
arrangementof an SieSi bond and bithienyleneedisilanylene unit as
arms is based on the Pd-catalyzed SuzukieMiyaura cross-coupling
reaction [9]. The starting compound, 2,4,6-tris[5-(1,3-dioxa-4,4,5,5-
*
Corresponding authors.
E-mail addresses: anaka@chem.kusa.ac.jp
zeus.eonet.ne.jp (M. Ishikawa).
(A.
Naka),
ishikawa-m@
0
022-328X/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2011.12.029

68
A. Naka et al. / Journal of Organometallic Chemistry 702 (2012) 67e72
tetramethyl-2-borolanyl)-2-thienyl]triazine (4) was prepared by
a series of the reactions, as shown in Schemes 1 and 2. First, we
synthesized 2,4,6-trithienyltriazine (2) by the Grignard cross-
coupling reaction, which was developed by Kumada and Tamao
We synthesized compound 4 by the two-step reaction using the
bromo compound 3 in 72% yield: conversion of 3 into the lithio
derivative by treating with n-BuLi, and the reaction of the resulting
lithio derivative with 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-
dioxaborolane (Scheme 2). All spectral data including mass
[
10]. Thus, the reaction of 2,4,6-trichlorotriazine (1) with thie-
nylmagnesium bromide in the presence of a catalytic amount of
NiCl (dppe) inTHFafforded compound 2 in 58% yield. Treatmentof 2
thus obtained with N-bromosuccinimide (NBS) in chloroform gave
,4,6-tris(5-bromothienyl)triazine (3) in 85% yield (Scheme 1). The
2
2
1
13
structures of 2 and 3 were verified by mass and H, C spectrometric
analysis, as well as byelemental analysis (see Experimental section).
Scheme 1.
Scheme 2.

A. Naka et al. / Journal of Organometallic Chemistry 702 (2012) 67e72
69
spectrum and also its elemental analysis are wholly consistent with
2.1. Optical properties of starlike molecules 5 and 7
those of the structure proposed for compound 4 (see Experimental
section).
The UVevisible absorption spectra and fluorescence spectra of
compounds 5 and 7 are summarized in Table 1, where the data for
relevant compounds, bithiophene, 2,4,6-tris(bithienyl)-1,3,5-
Compound 4 was used as the starting compound for the synthesis
of the starlike molecules with the arms extended to the three direc-
0
tions. The starlike compound, 2,4,6-tris(5 -pentamethyl-dis-
triazine (8), the starlike molecules having
a
1,3,5-
ilanylbithienyl)triazine (5) was prepared by the Pd-catalyzed cross-
coupling reaction of 2-(5-bromothienyl)pentamethyldisilane with 4.
The product 5 was isolated from the resulting reaction mixture, using
a silica gel column in 30% yield. The structure of 5 was confirmed by
dimethylsilylphenyl moiety as a core and the arms consisting of
a regular alternating arrangement of a siliconesilicon bond and
bithienylene unit (9 and 10), and a linear polymer with an alter-
native arrangement of a disilanylenebithienylene unit, poly[(tet-
raethyldisilanylene)bithienylene] (11) reported previously [12], are
also included for comparison (Figs. 1e3). The present starlike
molecules 5 and 7 show absorption maxima in the range of
398e399 nm. These bands are red-shifted by 60e80 nm from those
of the starlike molecules 9 and 10. In the fluorescence spectra, the
emission maximum of 5 and 7 display a marked red shift of about
60 nm compared with those of compounds 9 and 10. The quantum
yields of compounds 5 and 7 are much higher than those of 9 and
10, bithiophene, and poly[(tetraethyldisilanylene)bithienylene] 11.
The absorption bands and emission maxima of compounds 5 and 7
with the disilanyl groups shift bathochromically in comparison
with those of 8, which has no silyl groups. The electronic effects of
the silyl groups on the thiophene ring have been studied in terms of
the molecular orbital calculations by Kyushin et al. [13]. The bath-
1
13
29
mass and, H, C, and Si NMR spectrometric analysis. In fact, mass
spectrometric analysis for 5 indicates the molecular ion at m/z 963,
1
corresponding to the calculated value for C42
H
57
N
3
Si
6
S
6
. The H NMR
spectrum of 5 shows two signals at 0.14 and 0.41 ppm due to the two
13
kinds of methylsilyl protons, and thienyl ring protons. The C NMR
spectrum of 5 reveals two resonances at ꢀ2.8 and ꢀ2.4 ppm, attrib-
uted to the methylsilyl carbons, eight resonances at 124.6, 126.3,
132.4, 135.0, 139.4, 140.7, 142.0, and 144.0 ppm due to the thienyl ring
carbons and a single resonance at 167.0 ppm attributable to the
2
9
triazine carbon. The
Si NMR spectrum reveals two signals
at ꢀ23.7, ꢀ19.2 ppm, due to the two different kinds of the silicon
atoms. These results are wholly consistent with the structure
proposed for 5 (Schemes 3 and 4).
Similar methods were used for the synthesis of the molecules,
which have moreelongated
p-electron systems than those of5. Thus,
ochromic shift of the absorption band may be explained by
sep
the SuzukieMiyaura coupling of compound 4 with 1-(5-bromo-
thienyl)-2-bithienyltetramethyldisilane (6) [11] in MeOH gave
and *e * conjugation between the SieC(methyl) orbitals and
s
p
thiophene orbitals. The quantum yields of compounds 5 and 7 are
higher than that of 8. Compound 7 has a quantum yield of 0.96.
Mizuno et al. [14] have reported that the fluorescence intensities of
silyl-substituted aromatic compounds are stronger than those of
unsubstituted ones.
2
,4,6-tris(bithienyltetramethyldisilanylenebithienylene)triazine (7)
in 23% yield (Scheme 4). The structure of 7 was verified by mass and,
1
13
29
H, C, and Si NMR spectrometric analysis (see Experimental
section).
Scheme 3.
Scheme 4.

70
A. Naka et al. / Journal of Organometallic Chemistry 702 (2012) 67e72
Table 1
1.2
Absorption and emission data (in dioxane) for compounds 5 and 7 in comparison
with related compounds.
1
Compound (5)
Compound (7)
a
Compd
l
max
,
Abs (nm)
l
max
,
F
(nm)
F
F
0.8
5
7
398
399
303
386
321
335
343
451
452
362
437
388
0.67
0.96
0.018
0.57
0.39
0.41
0.33
0
.6
Bithiophene
8
9
0.4
0.2
1
1
0
1
381, 394
383, 397
0
a
-0.2
Based on quinine sulfate (
f
366 ¼ 0.546) as a standard.
350
400
450
500
550
600
Wavelength (nm)
In conclusion, the starlike molecules that have a triazine unit as
ꢀ5
Fig. 2. Fluorescence spectra of 5 and 7 in 10 M dioxane solution (
l
ex
¼
lUV-max).
a core and arms consisting of an alterative arrangement of an SieSi
bond and bithienylene unit were synthesized by the Pd-catalyzed
reactions of 2,4,6-tris[5-(1,3-dioxa-4,4,5,5-tetramethyl-2-borolanyl)-
magnesium sulfate. After the solvent was evaporated, compound 2
(6.607 g, 58% yield) was isolated by recrystallization with
hexaneechloroform (5:1) as an orange solid. Anal. Calcd for
C15H N S : C, 55.02; H, 2.77; N, 12.83. Found: C, 55.04; H, 2.49; N,
2
-thienyl]triazine with 5-bromothienyldisilanyl derivatives. In the
UVevis absorption and fluorescence spectra, 5 and 7 show absorption
maxima in a range of 398e399 nm, and reveal high fluorescence
quantum yields.
9
3 3
ꢁ
þ
1
12.47. Mp. 187 C; MS m/z 327 (M ); H NMR (
3
d CDCl ) 7.22 (t, 3H,
J ¼ 4.6 Hz, thienyl ring protons) 7.63 (d, 3H, J ¼ 4.6 Hz, thienyl ring
13
3
. Experimental
protons), 8.29 (d, 3H, J ¼ 4.6 Hz, thienyl ring protons); C NMR (
d
CDCl ) 128.4, 131.7, 132.3, 141.5 (thienylene carbons), 167.7 (triazine
3
3.1. General procedures
carbon).
All reactions were performed under an atmosphere of dry
3.1.2. 2,4,6-Tris(bromothienyl)-1,3,5-triazine (3)
nitrogen. NMR spectra were recorded on a JNM-LA300 spectrom-
eter and JNM-LA500 spectrometer. Low-resolution mass spectra
were measured on a JEOL Model JMS-700 instrument. High-
resolution mass spectra were obtained from a Thermo Fisher
Scientific LTQ Orbitrap XL. UVevisible absorption spectra were
measured with a JASCO V-560 spectrometer in dioxane. Fluores-
cence spectra were measured with a JASCO FP-777 spectrometer in
dioxane. Melting points were measured with a Yanaco-MP-S3
apparatus. Column chromatography was performed by using
Wakogel C-300 (WAKO). Diethyl ether and THF used as the solvents
were distilled from sodium/benzophenone ketyl, just before use.
In a 100 mL two-necked flask was placed 1.023 g (3.10 mmol) of
compound 1 in 50 mL of chloroform. To this was added 6.563 g
(36.9 mmol) of N-bromosuccinimide (NBS). The mixture was stir-
red for 6 days at room temperature and hydrolyzed with dilute
aqueous hydrochloric acid. The organic layer was separated,
washed with water and dried over anhydrous magnesium sulfate.
After the solvent was evaporated, compound 3 (1.485 g, 85% yield)
was isolated by recrystallization from chloroform as a white solid.
Anal. Calcd for C15
32.03; H, 1.00; N, 7.38. Mp. 243 C; MS m/z 561 (M ); H NMR (
CDCl
6 3 3 3
H N S Br : C, 31.94; H, 1.07; N, 7.45. Found: C,
ꢁ
þ
1
d
3
) 7.17 (d, 3H, J ¼ 4.0 Hz, thienyl ring protons) 7.96 (d, 3H,
13
J ¼ 4.0 Hz, thienyl ring protons); C NMR (
d
CDCl
3
) 120.7, 131.6,
3.1.1. 2,4,6-Trithienyl-1,3,5-triazine (2)
132.0, 142.1 (thienylene carbons), 166.7 (triazine carbon).
In a 300 mL two-necked flask equipped with a stirrer, reflux
condenser, and dropping funnel was placed a solution of 2-
thienylmagesium bromide prepared from 3.768 g (0.155 mol) of
magnesium and 25.340 g (0.155 mol) of 2-bromothiophene in
3.1.3. Synthesis of compound 4
In a 200 mL two-necked flask equipped with a stirrer, reflux
condenser, and dropping funnel was placed 1.721 g (3.05 mmol) of
compound 2 in 100 mL of THF. To this was added 3.45 mL
2
00 mL of THF. To this was added 0.831 g (1.59 mmol) of
NiCl
2
(dppe) and then 6.466 g (34.5 mmol) of 2,4,6-trichloro-1,3,5-
(13.78 mmol) of
a
1.54
M
n-butyllithiumehexane solution
ꢁ
ꢁ
triazine in 30 mL of THF. The mixture was heated to reflux for 12 h
and hydrolyzed with dilute aqueous hydrochloric acid. The organic
layer was separated, washed with water and dried over anhydrous
at ꢀ80 C. The mixture was stirred for 1 h at ꢀ80 C, and then to this
was added 2.456
g (13.27 mmol) of 2-isopropoxy-4,4,5,5-
tetramethy-1,3,2-dioxaborolane in 5 mL of THF. The mixture was
stirred overnight at room temperature and hydrolyzed with dilute
aqueous hydrochloric acid. The organic layer was separated,
washed with water and dried over anhydrous magnesium sulfate.
After the solvent was evaporated, compound 4 (1.613 g, 72% yield)
was isolated by recrystallization from hexane as a yellow solid.
1
.2
1
Compound (5)
Compound (7)
0
0
0
0
.8
.6
.4
.2
0
Anal. Calcd for C33
6.60; H, 6.21; N, 5.69. Mp. >300 C; MS m/z 705 (M ); H NMR (
CDCl ) 1.38 (s, 36H, CH
), 7.68 (d, 3H, J ¼ 3.4 Hz, thienyl ring
protons), 8.28 (d, 3H, J ¼ 3.4 Hz, thienyl ring protons); C NMR (
CDCl ) 24.8 (CH ), 84.8 (CO), 132.2, 137.6, 147.5 (thienylene
carbons), 167.7 (triazine carbon).
42 3 3 6 3
H B N O S : C, 56.19; H, 6.00; N, 5.96. Found: C,
ꢁ
þ
1
5
d
3
3
13
d
3
3
-
0.2
3
.1.4. Synthesis of compound 5
In a 200 mL two-necked flask was placed 1.012 g (1.43 mmol) of
250
300
350
400
450
500
550
600
Wavelength (nm)
compound 3, 1.529 g (5.21 mmol) of 2-(5-bromothienyl)pentam-
ethyldisilane, 0.107 g (0.152 mmol) of bis(triphenylphosphine)
Fig. 1. UVevis spectra of 5 and 7 in 10 5 M dioxane solution.
ꢀ

A. Naka et al. / Journal of Organometallic Chemistry 702 (2012) 67e72
71
Me
Me
Me
Me
Me
Me
T
Si
Si
Si
Si
H
H
Me
T
Me
T
T
Me
T
Me Me
T
Me
T
N
T
Si
T
Si
Me
Me
N
N
Me Si Me
T
T
H
8
T
Me Si Me
Me Si Me
Me
9
T =
S
H
H
T
T
Me
Si
T
Me
Me
T
Me
Si
Si
Si
T
Me
Me
T
Me Me
T
Me
T
Me
Si
Si
Me
Et Et
Si Si
Me
T
T
Et Et
Me Si Me
T
n
11
T
Me Si Me
Me Si Me
T
T
H
10
Fig. 3. Structures of compounds 8e11.
dichloropalladium and 1.708 g (5.20 mmol) of cesium carbonate in
0 mL MeOH. The mixture was heated to reflux for 3 h and
warmed to room temperature and stirred for 2 h. To this was slowly
added 5.81 g (18.52 mmol) of 2-(5,2 -bithiophen-2-yl)-1-chloro-
0
5
hydrolyzed with dilute aqueous hydrochloric acid. The organic
layer was separated, washed with water and dried over anhydrous
magnesium sulfate. After the solvent was evaporated, compound 5
1,1,2,2-tetramethyldisilane at room temperature. This mixture was
stirred overnight and hydrolyzed with dilute aqueous hydrochloric
acid. The organic layer was separated, washed with water and dried
over anhydrous magnesium sulfate. After the solvent was evapo-
rated, compound 6 (5.122 g, 62% yield) was isolated by a silica gel
column eluting with hexane as a yellow liquid. Anal. Calcd for
(
0.415 g, 30% yield) was isolated by a silica gel column eluting with
hexaneechloroform (1:1) as a green yellow solid. Exact mass calcd
ꢁ
for C42
m/z 964 (M ); H NMR (
Me
Si), 7.13 (d, 3H, J ¼ 3.4 Hz, thienyl ring protons), 7.27 (d, 3H,
J ¼ 3.4 Hz, thienyl ring protons), 7.43 (d, 3H, J ¼ 3.4 Hz, thienyl ring
H
58
N
3
Si
6
S
6
: 964.15558, found: 964.15651. Mp. >300 C; MS
þ
1
d
CDCl
3
) 0.14 (s, 27H, Me
3
Si), 0.41 (s, 18H,
16 2 3
C H19Si S Br: C, 43.32; H, 4.32. Found: C, 43.08; H, 4.15. MS m/z
þ
1
2
442 (M ); H NMR (d CDCl ) 0.38 (s, 6H, Me Si), 0.41 (s, 6H, Me Si),
3 2 2
6.90 (d, 1H, J ¼ 3.7 Hz thienyl ring protons), 7.01 (t, 1H, J ¼ 3.7 Hz
thienyl ring protons), 7.04 (d, 1H, J ¼ 3.7 Hz thienyl ring protons),
7.08 (d, 1H, J ¼ 3.7 Hz thienyl ring protons), 7.18 (d, 1H, J ¼ 3.7 Hz
thienyl ring protons), 7.21 (d, 1H, J ¼ 3.7 Hz thienyl ring protons),
13
protons), 8.16 (s, 3H, 3.4 Hz, thienyl ring protons); C NMR (
CDCl
) ꢀ2.8, ꢀ2.4 (MeSi), 124.6, 126.3, 132.4, 135.0, 139.4, 140.7,
42.0, 144.0 (thienylene carbons), 167.0 (triazine carbon); Si NMR
CDCl
) ꢀ23.7, ꢀ19.2.
d
3
2
9
1
1
3
(d
3
7.23 (d, 1H, J ¼ 3.7 Hz thienyl ring protons);
C NMR (d
CDCl
134.9, 135.3, 136.7, 137.2, 140.7, 142.8 (thienylene carbons); Si
NMR( CDCl
) ꢀ24.5, ꢀ24.1.
3
) ꢀ3.0, ꢀ2.9 (MeSi), 116.8, 123.7, 124.3, 125.1, 127.7, 131.3,
29
3
.1.5. Synthesis of 1-(5-bromothienyl)-2-bithienyltetramethyldi-
silane (6)
In a 100 mL two-necked flask was placed 4.69 g (19.14 mmol) of
,5-dibromothiophene in 50 mL of diethyl ether. To this was added
d
3
2
3.1.6. Synthesis of compound 7
1
1.5 mL (19.00 mmol) of a 1.65 M n-butyllithiumehexane solution
In a 100 mL two-necked flask was placed 0.507 g (0.719 mmol)
of compound 4, 1.197 g (2.70 mmol) of compound 6, 0.054 g
ꢁ
at ꢀ40 C. After the addition was complete, the mixture was

72
A. Naka et al. / Journal of Organometallic Chemistry 702 (2012) 67e72
(
0
0.08 mmol) of bis(triphenylphosphine)dichloropalladium and
.853 g (2.59 mmol) of cesium carbonate in 50 mL MeOH. The
(i) S. Kotha, K. Chakraborty, E. Brahmachary, Synlett 10 (1999) 1621;
(
(
j) F. Cherioux, L. Guyard, P. Audedebert, Chem. Commun. (1998) 2225;
k) E. Rebourt, B. Pepin-Donut, E. Dinh, Polymer 36 (1995) 399.
mixture was heated to reflux for 3 h and hydrolyzed with dilute
aqueous hydrochloric acid. The organic layer was separated,
washed with water and dried over anhydrous magnesium sulfate.
After the solvent was evaporated, compound 7 (0.230 g, 23% yield)
was isolated by a silica gel column eluting with hexaneechloroform
[
[
2] O.V. Borshchev, S.A. Ponomarenko, N.M. Surin, M.M. Kaptyug, M.I. Buzin,
A.P. Preshkova, N.V. Demchenko, V.D. Myakushev, A.M. Muzafarov, Organo-
metallics 26 (2007) 5165.
3] (a) M. Ishikawa, K.-K. Lee, W. Schneider, A. Naka, T. Yamabe, Y. Harima,
T. Takeuchi, Organometallics 19 (2000) 2406.
[4] M. Ishikawa, H. Teramura, K.-K. Lee, W. Schneider, A. Naka, H. Kobayashi,
Y. Yamaguchi, M. Kikugawa, J. Ohshita, A. Kunai, H. Tang, Y. Harima,
T. Yamabe, T. Takeuchi, Organometallics 20 (2001) 5331.
[
[
[
[
(
2:1) as a green yellow solid. Exact mass calcd for C63
414.03308, found: 1414.03588. Mp. >300 C; MS m/z 1413 (M );
H
64
N
3
Si
6
S
12
:
ꢁ
þ
1
5] A. Naka, Y. Matsumoto, T. Itano, K. Hasegawa, T. Shimamura, J. Ohshita,
A. Kunai, T. Takeuchi, M. Ishikawa, J. Organomet. Chem. 694 (2009) 346.
6] T. Sonoda, H. Rahmat, M. Ozaki, K. Yoshino, W. Schneider, K.-K. Lee, A. Naka,
M. Ishikawa, Appl. Phys. Lett. 75 (1999) 2193.
7] J. Ohshita, Y. Izumi, D.-H. Kim, A. Kunai, T. Kosuge, Y. Kunugi, A. Naka,
M. Ishikawa, Organometallics 26 (2007) 6150.
1
H NMR (
H, J ¼ 3.4 Hz, thienyl ring protons), 7.07 (d, 3H, J ¼ 3.4 Hz, thienyl
ring protons), 7.12 (d, 3H, J ¼ 3.4 Hz, thienyl ring protons), 7.19 (d,
H, J ¼ 3.4 Hz, thienyl ring protons), 7.21 (d, 3H, J ¼ 3.4 Hz, thienyl
ring protons), 7.25 (d, 3H, J ¼ 3.4 Hz, thienyl ring protons), 7.28 (d,
H, J ¼ 3.4 Hz, thienyl ring protons), 7.43 (d, 3H, J ¼ 3.4 Hz, thienyl
3 2 2
d CDCl ) 0.45 (s, 18H, Me Si), 0.46 (s, 18H, Me Si) 7.01 (t,
3
3
8] (a) K.M. Omar, S.-Y. Ku, Y.-C. Chen, K.-T. Wong, A.J. Bard, J. Am. Chem. Soc. 132
(
(
2010) 10944;
3
b) L. Llies, Y. Sato, C. Mitsui, H. Tsuji, E. Nakamura, Chem. Asian. J. 5 (2010)
13
ring protons), 8.17 (d, 3H, J ¼ 3.4 Hz, thienyl ring protons); C NMR
CDCl
) ꢀ2.9, ꢀ2.8 (MeSi), 123.8, 124.4, 124.8, 125.2, 126.4, 127.8,
32.5, 135.4, 135.5, 137.1, 137.3, 139.4, 139.5, 142.3, 142.9, 144.0
1376;
(d
3
(c) Y. Hisamatsu, H. Aihara, Chem. Commun. 46 (2010) 4902;
(
(
(
d) S. Ren, D. Zeng, H. Zhong, Y. Wang, S. Qian, Q. Fang, J. Phys. Chem. B 114
2010) 10374;
e) H.-F. Chen, S.-J. Yang, Z.-H. Tsai, W.-Y. Hung, T.-C. Wang, K.-T. Wong,
1
2
9
(
thienylene carbons), 167.1 (triazine carbon);
Si NMR(d
CDCl
3
) ꢀ24.4, ꢀ24.2.
J. Mater. Chem. 19 (2009) 8112;
f) L. Zou, Z. Liu, X. Yan, Y. Liu, Y. Fu, J. Liu, Z. Huang, X. Chen, J. Qin, Eur. J. Org.
Chem. (2009) 5587;
g) P. Leriche, F. Piron, E. Ripaud, P. Frere, M. Allain, J. Roncali, Tetrahedron
(
Acknowledgments
(
Lett. 50 (2009) 5673;
We appreciate the Asahi Glass Foundation and Electric Tech-
nology Research Foundation of Chugoku for financial support. We
also thank Shin-Etsu Chemical Co., Ltd. for the gift of chlorosilanes.
The measurement of High-resolution mass spectra was made using
LTQ Orbitrap XL at the Natural Science Center for Basic Research
and Development (N-BARD), Hiroshima University.
(h) H. Meier, E. Karpuk, H.C. Holst, Eur. J. Organomet. Chem. (2006) 2609;
(
(
(
i) H. Meier, H.C. Holst, A. Oehlhof, Eur. J. Organomet. Chem. (2003) 4173;
j) J. Pang, Y. Tao, S. Freiberg, X. Yang, M. D’lorio, S. Wang, J. Mater. Chem. 12
2002) 206;
(k) S. Brasselet, F. Cherioux, P. Audebert, J. Zyss, Chem. Mater. 11 (1999) 1915;
l) F. Cherioux, P. Audebert, P. Hapiot, Chem. Mater. 10 (1998) 1984.
9] (a) A. Suzuki, Angew. Chem. Int. Ed. 50 (2011) 6722;
(
[
(
(
b) S. Kotha, K. Lahiri, D. Kashinath, Tetrahedron 58 (2002) 9633;
c) A. Suzuki, J. Organomet. Chem. 576 (1999) 147;
References
(d) N. Miyaura, A. Suzuki, Chem. Rev. 95 (1995) 2457.
10] (a) M. Netherton, G. Fu, Adv. Syn. Catal. 346 (2004) 1525;
b) A. Hillier, G. Grasa, M. Viciu, H. Lee, C. Yang, S. Nolan, J. Organomet. Chem.
53 (2002) 69;
c) J. Huang, S. Nolan, J. Am. Chem. Soc. 121 (1999) 9889.
11] J. Ohshita, D. Kanaya, M. Ishikawa, Appl. Organomet. Chem. 7 (1993) 269.
12] (a) A. Kunai, T. Ueda, K. Horata, E. Toyoda, I. Nagamoto, J. Ohshita, M. Ishikawa,
Organometallics 15 (1996) 2000;
[
(
6
(
[1] (a) A.L. Kanibolotsky, I.F. Perepichka, P.J. Skabara, Chem. Soc. Rev. 39 (2010)
2695;
(
(
b) J. Liu, S. Zhang, W.-X. Zhang, Z. Xi, Organometallics 28 (2009) 413;
c) S. Roquet, A. Cravino, P. Leriche, O. Alévêque, P. Frère, J. Roncali, J. Am.
[
[
Chem. Soc. 128 (2006) 3459;
d) A.L. Kanibolotsky, R. Berridge, P.J. Skabara, I.F. Perepichka, D.D.C. Bradley,
M. Koeberg, J. Am. Chem. Soc. 126 (2004) 13695;
(
(b) H. Tang, L. Zhu, Y. Harima, K. Yamashita, K.-K. Lee, A. Naka, M. Ishikawa,
J. Chem. Soc., Perkin Trans. 2 (2000) 1976.
(
(
(
e) J. Pei, J.-L. Wang, X.-Y. Cao, X.-H. Zhou, W.-B. Zhang, J. Am. Chem. Soc. 125
2003) 9944;
f) S.A. Ponomarenko, S. Kirchmeyer, A. Elshner, B.-H. Huisman, A. Karbach,
[
[
13] S. Kyushin, T. Matsuura, H. Matsumoto, Organometallics 25 (2006) 2761.
14] (a) K. Asai, G.-I. Konishi, K. Sumi, K. Mizuno, J. Organomet. Chem. 696 (2011)
1
(
236;
b) H. Maeda, H. Ishida, Y. Inoue, A. Merpuge, T. Maeda, K. Mizuno, Res. Chem.
Intermed. 35 (2009) 939.
D. Drechsler, Adv. Funct. Mater. 13 (2003) 591;
(
(
g) M. Thelakkat, Macromol. Mater. Eng. 287 (2002) 442;
h) F. Cherioux, L. Guyard, Adv. Funct. Mater. 11 (2001) 305;