Nanosized starlike molecules. Synthesis and optical properties of tris- and tetrakis[oligo(disilanylenebithienylene)dimethylsilyl]benzene

Article abstract of DOI:10.1016/j.jorganchem.2008.10.053

The syntheses of two types of starlike molecules with the arms that extend to three and four directions have been reported. The molecules with the arms consisting of a regular alternating arrangement of a silicon-silicon bond and bithienylene unit that ex

Full text of DOI:10.1016/j.jorganchem.2008.10.053

Journal of Organometallic Chemistry 694 (2009) 346–352
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Nanosized starlike molecules. Synthesis and optical properties
of tris- and tetrakis[oligo(disilanylenebithienylene)dimethylsilyl]benzene
a
a
a
a
Akinobu Naka a, , Yoshiaki Matsumoto , Tatsuya Itano , Kei Hasegawa , Tomoaki Shimamura ,
*
Joji Ohshita b, Atsutaka Kunai b, Takae Takeuchi c, Mitsuo Ishikawa a,
*
a Department of Life Science, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajima-cho, Kurashiki, Okayama 712-8505, Japan
b Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan
c Department of Chemistry, Faculty of Science, Nara Women’s University, Nara 630-8506, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
The syntheses of two types of starlike molecules with the arms that extend to three and four directions
have been reported. The molecules with the arms consisting of a regular alternating arrangement of a sil-
icon–silicon bond and bithienylene unit that extend to three directions were synthesized by the reactions
of 1,3,5-tris(chlorodimethylsilyl)benzene, which was chosen as a core, with the lithio[oligo(disilanyle-
nebithienylene)] derivatives. The starlike molecules with extended arms to four directions were prepared
by the reaction of 1,2,4,5-tetrakis(fluorodimethylsilyl)benzene used as a core, with lithio[oligo(disilany-
lenebithienylene)]s. UV–Vis absorption and fluorescence properties of these starlike molecules have been
investigated in a dioxane solution. The present molecules showed absorption maxima in a range of 321–
337 nm, and revealed higher fluorescence quantum yields than that of the corresponding linear polymer,
poly[(tetraethyldisilanylene)bithiophene].
Received 5 September 2008
Received in revised form 10 October 2008
Accepted 14 October 2008
Available online 6 November 2008
Keywords:
Starlike molecules
Disilanylenebithienylene
UV absorption
Photoluminescence
Quantum yield
Ó 2008 Elsevier B.V. All rights reserved.
1. Introduction
starlike molecules bearing bithienylene–silylene units in the arms
and investigated their optical properties [3e].
Three-dimensional, organometallic dendrimers containing
p
-
We have reported the synthesis of two types of the nano-
sized, starlike molecules. One of them is the molecules bearing
the arms consisting of a regular alternating arrangement of a sil-
icon–silicon bond and bithienylene unit, which extend to three
directions (see Chart 1). The other is silicon-containing starlike
compounds with oligothienylene units (bithienylene to hexath-
ienylene) [5]. As can be expected from the unique molecular
structure, the starlike molecules display novel optical properties.
For examples, they reveal high fluorescence quantum yields and
long lifetimes of the excited state [5,6]. We also have reported
that these molecules can be used as the functional devices such
as optical recording materials [7] and semiconductors in field-ef-
fect transistors [8].
conjugated system have attracted a great deal of attention owing
to their unique physical and chemical properties and also to their
potential application in organic photo- and electroluminescent de-
vices, and many types of the dendrimers have been synthesized to
date [1]. In the field of organosilicon chemistry, several types of
dendrimers whose framework is composed of the silicon–silicon
bonds, silicon–oxygen bonds, and silicon–carbon bonds, have been
reported [2,3].
On the other hand, starlike compounds with the arms that ex-
tend to three directions have attracted much attention, because
they show interesting properties, depending on their unique
molecular structure, and may be used as functionality materials.
Several types of the starlike molecules with conjugated
p
-electron
We have investigated so far optical properties of many types
of the starlike molecules with the same core, tris(dimethylsi-
lyl)methylsilane unit, but with different arms. We considered
that the starlike molecules bearing aromatic ring system as a
core might show better optical behavior than those with the
tris(silyl)silane moiety reported previously. In this paper we
report first synthesis of new types of the starlike molecules
bearing a poly(silyl)-substituted benzene ring as a core, 1,3,5-
tris- and 1,2,4,5-tetrakis[oligo(disilanylenebithienylene)dimethyl-
silyl]benzene, and their UV–Vis absorption and fluorescence
spectra.
system in their arms have been synthesized and their optical prop-
erties have been examined [4]. However, little interest has been
shown in the chemistry of the starlike molecules including both
silylene unit and
p-electron system in their arms. Recently, Pon-
omarenko and his coworkers have reported the synthesis of the
* Corresponding authors.
E-mail addresses: anaka@chem.kusa.ac.jp (A. Naka), ishikawa-m@zeus.eonet.
ne.jp (M. Ishikawa).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.10.053

A. Naka et al. / Journal of Organometallic Chemistry 694 (2009) 346–352
347
a bithienyl unit as an end-group. As reported previously, the
reaction of chloropentamethyldisilane with 50-bromo-5-lithiobi-
thiophene in diethyl ether afforded (50-bromo-2,20-bithiophen-5-
yl)pentamethyldisilane (3) in 70% yield [5a]. Similarly, 1-(50-bro-
mo-2,20-bithiophen-5-yl)-2-[50-(pentamethyldisilanyl)-2,20-bithio-
phen-5-yl]tetramethyldisilane (6) was prepared by the reaction of
50-bromo-5-lithiobithiophene with 1,2-dichlorotetramethyldisi-
lane, followed by treatment of the resulting chloro compound 5
with a lithio derivative 4 prepared from 3 and n-butyllithium in
73% yield. Bromo compound 8 with a longer disilanylenebithienyl-
ene unit than 6 was obtained by the reaction of lithio compound 7,
generated from 6 and n-butyllithium, with 5 in 73% yield.
Similar methods were used for the syntheses of the arms with a
bithienylene end-group. Thus, treatment of compound 5 with lith-
iobithiophene in diethyl ether gave 1-(2,20-bithiophen-5-yl)-2-(50-
bromo-2,20-bithiophen-5-yl)tetramethyldisilane (10) in 81% yield.
Treatment of lithio compound 11, prepared by the reaction of 10
with n-butyllithium, with compound 5 produced 1-(2,20-bithio-
phen-5-yl)-2-[50-(2-(50-bromo-2,20-bithiophen-5-yl)tetramethyldi-
silanyl)-2,20-bithiophen-5-yl]tetramethyldisilane (12) in 82% yield.
The structures of compounds 3, 6, 8, 10, and 12, used for construct-
ing the arms were confirmed by spectrometric analysis, as well as
by elemental analysis.
Me Me
Si Si
Me Me
S
S
S
S
S
Me2Si
Me2Si
MeSi
MeSi
X = 0, 1, 2
x
3
SiMe2(t-Bu)
X = 2, 3, 4
x
x
3
S
S
S
Me2Si
MeSi
SiMe2(t-Bu)
X = 2, 3
2
3
n-Bu
Chart 1.
2. Results and discussion
The method used for the synthesis of the present starlike mol-
ecules is based on the reaction of 1,3,5-tris(chlorodimethylsi-
lyl)benzene (1) and 1,2,4,5-tetrakis(fluorodimethylsilyl)benzene
(2) with the lithio[oligo(disilanylenebithienylene)] derivatives.
Compound, 1,3,5-tris(chlorosilyl)benzene (1), used as a core for
the synthesis of the molecules with the extended arms to three
directions, was prepared by the reaction of 1,3,5-tribromobenzene
with chlorodimethylsilane in the presence of magnesium in a THF
solution, followed by the reaction of the resulting 1,3,5-
tris(dimethylsilyl)benzene with carbon tetrachloride in the pres-
ence of a catalytic amount of palladium dichloride in high yield,
as shown in Scheme 1. Similarly, the starting compound 2, used
for the synthesis of the starlike molecules consisting of four arms,
was synthesized by the reaction of 1,2,4,5-tetrabromobenzene
with dimethylchlorosilane in the presence of magnesium in THF,
and then chlorination of the resulting tetrakis(dimethylsilyl)ben-
zene with chlorine gas. Finally, treatment of 1,2,4,5-tetrakis(chlo-
rodimethylsilyl)benzene with zinc fluoride afforded the core
compound 2 in high total yield [9]. The structures of 1 and 2 were
verified by mass and 1H, 13C, and 29Si NMR spectrometric analysis,
as well as by elemental analysis (see Section 3).
2.1. 1,3,5-Tris[oligo(disilanylenebithienylene)dimethylsilyl]benzenes
The starlike compounds whose arms extend to three directions
were synthesized by the reaction of 1,3,5-tris(chlorosilyl)benzene
(1) with the respective lithio derivatives obtained by treatment
of compounds 3, 6, and 8, with n-butyllithium. Thus, the reaction
of 1 with lithio compound 4, generated from 3 and n-butyllithium
in diethyl ether, afforded 1,3,5-tris[dimethyl(50-pentamethyldisila-
nyl)-2,20-bithiophen-5-yl]benzene (14) as shown in Scheme 3. The
product 14 was isolated from the reaction mixture, using a silica
gel column in 62% yield. The structure of 14 was confirmed by
mass and, 1H, 13C, and 29Si NMR spectrometric analysis. In fact,
mass spectrometric analysis for 14 indicates the presence of a
molecular ion at m/z 1134, corresponding to the calculated value
for C51H78Si9S6. The 29Si NMR spectrum reveals three signals at
ꢀ24.1, ꢀ19.3, and ꢀ11.3 ppm, due to three different kinds of the
silicon atoms. These results are wholly consistent with the struc-
ture proposed for 14.
The syntheses of two types of the arms having an alternative
arrangement of a silicon–silicon bond and bithienylene unit were
carried out as shown in Scheme 2. One of them is the arms that
have a terminal disilanyl group, while the other is the arms bearing
Treatment of 1 with the lithio derivative 7 generated from bro-
mo compound 6 gave starlike molecule 15 in 62% isolated yield.
Mass spectrometric analysis for 15 shows a parent ion at m/z
Br
Br
HMe2Si
SiMe2H
+
+
3 Mg
3 Me2SiHCl
Br
SiMe2H
HMe2Si
SiMe2H
ClMe2Si
SiMe2Cl
cat. PdCl2
CCl4
SiMe2H
SiMe2Cl
1
Br
Br
Br
Br
HMe2Si
SiMe2H
+
+
4 Mg
4 Me2SiHCl
HMe2Si
ZnF2
SiMe2H
ClMe2Si
ClMe2Si
SiMe2Cl
SiMe2Cl
FMe2Si
FMe2Si
SiMe2F
SiMe2F
HMe2Si
HMe2Si
SiMe2H
SiMe2H
Cl2
CCl4
2
Scheme 1.

348
A. Naka et al. / Journal of Organometallic Chemistry 694 (2009) 346–352
Me3SiSiMe2Cl
n-BuLi
Br
T
T
T
Li
Br
T
T
SiMe2SiMe3
Li T T SiMe2SiMe3
3
4
MeMe
Si Si
MeMe
Me Me
Si Si Me
Me Me
4
ClMe2SiSiMe2Cl
Br
T
Li
Br
T
T
SiMe2SiMe2Cl
Br
T
T
T
T
T
T
5
6
MeMe
Me Me
Si Si Me
Me Me
MeMe
Si Si
MeMe
Me Me
Si Si
Me Me
8
Me Me
5
n-BuLi
n-BuLi
Li
T
T
Si Si
T
T
Br
T
T
T
T
Si Si Me
Me Me
MeMe
7
MeMe
Si Si
Me Me
Me Me
Li
T
T
T
T
Si Si
Me Me
9
T
T
T
Si Si Me
Me Me
MeMe
MeMe
MeMe
Si Si
H
T
T
Li
n-BuLi
Br
T
T
SiMe2SiMe2Cl
Br
T
Si Si
T
T
H
Li
T
T
T
T
H
MeMe
MeMe
5
10
11
MeMe
Si Si
Me Me
Si Si
MeMe
Si Si
Me Me
Si Si T T H
5
n-BuLi
Br
T
T
T
T
T
T
H
Li
T
T
T
T
MeMe
Me Me
MeMe
Me Me
12
13
T =
S
Scheme 2.
Me2Si
C6H3
T
T
SiMe2SiMe3)3
MeMe
+
3
3
C6H3(
Li
Li
T
T
T
T
SiMe2SiMe3
1
4
14
MeMe
Si Si
Me Me
Si Si Me
Me Me
Me Me
Si Si Me
Me Me
1
1
+
+
T
T
Me2Si
T
T
Si Si
T
T
MeMe
MeMe
3
7
15
MeMe
Si Si
Me Me
Si Si
Me Me
Me Me
Si Si Me
Me Me
Li
T
T
T
T
T
T
3
MeMe
9
MeMe
Si Si
MeMe
Me Me
Si Si
Me Me
Me Me
Si Si Me
Me Me
C6H3
Me2Si
T
T
T
T
T
T
T
3
16
MeMe
MeMe
Si Si T T H
1
+
3
C6H3
Me2Si
Li
T
T
Si Si
MeMe
11
T
T
H
T
MeMe
3
17
MeMe
Si Si
MeMe
Me Me
Si Si
Me Me
MeMe
Si Si
MeMe
Me Me
Si Si T T H
Me Me
Me2Si
C6H3
T
T
T
T
T
T H
+
Li
T
T
T
T
1
3
3
18
13
Scheme 3.
1974, which is consistent with the calculated molecular weight of
the proposed structure. Its 29Si NMR spectrum reveals five signals
at ꢀ24.6, ꢀ24.5, ꢀ24.1, ꢀ19.3, and ꢀ11.3 ppm, attributable to five
different kinds of the silicon atoms, as expected. Likewise, the core
compound 1 reacted with the lithio derivative produced from 8
and n-butyllithium in diethyl ether, to give starlike compound 16
in 13% isolated yield. Mass spectrometric analysis for 16 indicates
a molecular ion at m/z 2814, which is consistent with the calcu-
lated molecular weight for 16. Its 29Si NMR spectrum reveals a
overlapping signal at ꢀ24.6 ppm, due to four silicon atoms, and

A. Naka et al. / Journal of Organometallic Chemistry 694 (2009) 346–352
349
Table 1
three signals at ꢀ24.1, ꢀ18.3, and ꢀ11.3 ppm. These results are
wholly consistent with the structure proposed for 16.
Absorption and emission data (in dioxane) for compounds 14–20 in comparison with
related compounds.
The starlike compounds bearing a bithienyl moiety as an end-
group were prepared by the similar methods to those used for
the synthesis of 14–16. Thus, the reaction of 1 with lithio com-
pound 11, derived from treatment of bromo compound 10 with
n-butyllithium in diethyl ether, afforded starlike molecule 17,
while with the lithio derivative 13, arising from the reaction of
12 with n-butyllithium, compound 1 reacted to give the product
(18) in 31% yield. The structures of 17 and 18 were verified by mass
and, 1H, 13C, and 29Si NMR spectrometric analysis, as well as by ele-
mental analysis (see Section 3).
Compound
kmax,Abs
(nm)
kmax,F
(nm)
U
F(ns)a
14
15
16
17
18
19
20
321
337
333
335
328
334
336
325
336
329
332
343
388
384, 396
397
381, 394
380, 391
397
398
390
381, 398
398
386, 398
383, 397
0.39
0.68
0.73
0.41
0.74
0.46
0.74
0.23
0.68
0.71
0.75
0.33
SiSiTTSiSib
21c
22d
23e
24f
2.2. 1,2,4,5-Tetrakis[oligo(disilanylenebithienylene)dimethylsilyl]-
benzenes
a
Based on quinine sulfate (/366 = 0.546) as a standard.
Me3SiMe2SiTTSiMe2SiMe3 T = thienylene.
MeSi(SiMe2TTSiMe2SiMe3)3 T = thienylene.
MeSi(SiMe2TTSiMe2SiMe2TTH)3 T = thienylene.
MeSi(SiMe2TTSiMe2SiMe2TTSiMe2SiMe2TTH)3 T = thienylene.
Poly[(tetraethyldisilanylene)bithiophene].
b
c
d
e
f
For the synthesis of starlike molecule 19, we first carried out the
reaction of 1,2,4,5-tetrakis(chlorodimethylsilyl)benzene with lithio
compound 11. However, no starlike molecule was obtained at all.
We thought that the bulky chlorine atoms in the starting com-
pound would prevent the coupling reaction with the lithio com-
pound. Therefore, we used the fluoro derivative 2 as the starting
compound. Thus, treatment of 2 with the lithio derivative 11 in
diethyl ether afforded starlike molecule 19, with the extended
arms to four directions, in 27% isolated yield, as shown in Scheme
4.
The present starlike molecules 14–20 show absorption maxima
in the range of 321–337 nm. These results are similar to those of
the starlike molecules 21–23, reported previously [5a]. In their
fluorescence spectra, a similar tendency is also observed. The
quantum yields of compounds 14–20 are somewhat lower than
those of the starlike compounds 21–23, but much higher than
those of bithiophene and poly[(tetraethyldisilanylene)bithioph-
ene] (24). The higher quantum yields are probably due to the star-
like structure. The absorption and fluorescence maximum
wavelengths for 1,3,5-tris- and 1,2,4,5-tetrakis[oligo(disilanyle-
nebithienylene)dimethylsilyl]benzene are very close to each other.
The fluorescence quantum yields for these molecules also show a
striking resemblance to each other as shown in Table 1.
In conclusion, the starlike molecules with the arms consisting of
a regular alternating arrangement of a silicon–silicon bond and
bithienylene unit were readily synthesized by the reactions of
1,3,5-tris(chlorodimethylsilyl)benzene and 1,2,4,5-tetrakis(fluoro-
dimethylsilyl)benzene with the respective lithio[oligo(disilanyle-
nebithienylene)] derivatives. The starlike molecules whose arms
extend to three and four directions showed absorption maxima
in the range of 321–337 nm, and high fluorescence quantum
yields.
The structure of 19 was confirmed by mass and, 1H, 13C, and 29Si
NMR spectrometric analysis, and also by elemental analysis. Mass
spectrometric analysis for 19 shows a parent ion at m/z 2086, cor-
responding to the calculated value for C94H110Si12S6. The 29Si NMR
spectrum indicates a signal consisting of the two silicon atoms at
ꢀ24.4 and a signal at ꢀ9.0 ppm.
Similarly, treatment of 2 with lithio compound 13 gave starlike
molecule 20 in 7% isolated yield. The mass spectrum of the product
20 indicates a parent ion at m/z 3206, which is consistent with the
calculated molecular weight for the product 20. Its 29Si NMR spec-
trum reveals an overlapping signal consisting of the four silicon
atoms at ꢀ24.5 ppm, and a signal at ꢀ9.8 ppm. These results and
also other NMR spectral data described in Section 3 are wholly con-
sistent with the structures proposed for 19 and 20.
2.3. Optical properties of starlike molecules
The UV–Vis absorption spectra and fluorescence spectra of com-
pounds 14–20 are summarized in Table 1, where the data for bithi-
ophene, the starlike molecules having the arms consisting of a
regular alternating arrangement of a silicon–silicon bond and bith-
ienylene unit and a tris(dimethylsilyl)methylsilane moiety as a
core, 21–23, and a linear polymer with an alternative arrangement
3. Experimental
3.1. General procedures
of
a
disilanylene–bithienylene unit, poly[(tetraethyldisilanyl-
All reactions were performed under an atmosphere of dry nitro-
gen. NMR spectra were recorded on a JNM-LA300 spectrometer
and JNM-LA500 spectrometer. Low-resolution mass spectra were
ene)bithiophene] (24) reported previously, are also included for
comparison.
MeMe
MeMe
2
+
4
4
C6H2
Me2Si
Li
T
T
T
Si Si
MeMe
11
T
T
H
T
T
Si Si T T H
MeMe
19
4
MeMe
Si Si
Me Me
Si Si T T H
Me Me
MeMe
Si Si
Me Me
Si Si T T H
Me2Si
T
T
T
T
C6H2
Li
T
T
T
2
+
MeMe
MeMe
Me Me
4
20
13
Scheme 4.

350
A. Naka et al. / Journal of Organometallic Chemistry 694 (2009) 346–352
measured on a JEOL Model JMS-700 instrument. UV–Vis absorption
spectra were measured with a JASCO V-560 spectrometer in diox-
ane. Fluorescence spectra were measured with a JASCO FP-777
spectrometer in dioxane. Melting point was measured with a Yana-
co-MP-S3 apparatus. Column chromatography was performed by
using Wakogel C-300 (WAKO). Diethyl ether and THF used as a sol-
vent were distilled from sodium/benzophenone ketyl, just before
use.
sium sulfate. After the solvent was evaporated, compound 3
(24.31 g, 70% yield) was isolated by a silica gel column eluting with
hexane as a yellow viscous liquid. Anal. Calc. for C13H19Si2S2Br: C,
41.58; H, 5.10. Found: C, 41.53; H, 5.00%. MS m/z 374 (M+); 1H
NMR (d CDCl3) 0.12 (s, 9H, SiMe3), 0.38 (s, 6H, SiMe2), 6.91 (d,
1H, J = 3.7 Hz, thienylene proton), 6.95 (d, 1H, J = 3.7 Hz, thienylene
proton), 7.05 (d, 1H, J = 3.7 Hz, thienylene proton), 7.15 (d, 1H,
J = 3.7 Hz, thienylene proton); 13C NMR (d CDCl3) ꢀ2.9, ꢀ2.5
(Me3Si, Me2Si), 110.8, 123.6, 125.3, 130.6, 134.7, 139.0, 139.5,
141.3 (thienylene carbons); 29Si NMR (d CDCl3) ꢀ19.3, ꢀ23.9.
3.2. 1,3,5-Tris(dimethylsilyl)benzene
In a 200 mL two-necked flask was placed 2.81 g (0.12 mol) of
magnesium and 12.99 g (0.14 mol) of chlorodimethylsilane in
60 mL of THF. To this was added 10.26 g (32.6 mmol) of 1,3,5-trib-
romobenzene in 40 mL of THF. After the mixture was stirred for 5 h
at room temperature, it was hydrolyzed with dilute hydrochloric
acid. The organic layer was separated, washed with water, and
dried over anhydrous magnesium sulfate. After the solvent was
evaporated, the residue was distilled under reduced pressure to
give 5.41 g (66% yield) of pure 1,3,5-tris(dimethylsilyl)benzene.
Anal. Calc. for C12H24Si3: C, 57.06; H, 9.58. Found: C, 57.06; H,
9.50%. B.p. 56 °/1 torr; MS m/z 252 (M+); 1H NMR (d CDCl3) 0.40
(d, 18H, Me2Si, J = 3.7 Hz), 4.48 (sep, 3H, SiH, J = 3.7 Hz), 7.77 (s,
3H, phenylene ring protons); 13C NMR (d CDCl3) ꢀ3.7 (Me2Si),
135.9, 140.5 (phenylene ring carbons); 29Si NMR (d CDCl3) ꢀ16.7.
3.6. Preparation of compound 5
To a solution of 10.01 g (0.03 mol) of 5,50-dibromo-2,20-bithi-
ophene in 100 mL of diethyl ether was added 20.0 mL
(0.031 mol) of a 1.54 M n-butyllithium–hexane solution at ꢀ40 °C
over a period of 20 min. The resulting mixture was stirred at room
temperature for 5 h, and then 5.70 g (0.030 mol) of 1,2-dichlorote-
tramethyldisilane was added at ꢀ20 °C over a period of 30 min.
After filtration of the mixture, the solvent was evaporated, and
the residue was distilled under reduced pressure to give 7.24 g
(61% yield) of 5, as a bright yellow viscous liquid. Anal. Calc. for
C12H16Si2S2ClBr: C, 36.40; H, 4.07. Found: C, 36.10; H, 3.99%. B.p.
172–178 °C/1 torr; MS m/z 394 (M+); 1H NMR (d CDCl3) 0.10 (s,
6H, SiMe2), 0.12 (s, 6H, SiMe2), 6.53 (d, 1H, J = 3.7 Hz, thienylene
proton), 6.56 (d, 1H, J = 3.7 Hz, thienylene proton), 6.74 (d, 1H,
J = 3.7 Hz, thienylene proton), 6.78 (d, 1H, J = 3.7 Hz, thienylene
proton); 13C NMR (d CDCl3) ꢀ3.5, 1.9 (Me2Si), 111.1, 123.9, 125.5,
130.6, 135.7, 136.0, 138.6, 142.1 (thienylene carbons); 29Si NMR
(d CDCl3) ꢀ24.5, ꢀ21.2.
3.3. Preparation of compound 1
In a 100 mL two-necked was placed 0.350 g (1.97 mmol) of pal-
ladium chloride and 70 mL of carbon tetrachloride. To this was
added 5.41 g (21.46 mmol) of 1,3,5-tris(dimethylsilyl)benzene.
The mixture was heated to reflux for 5 h. After the solvent was
evaporated, the residue was distilled under reduced pressure to
give 5.27 g (69% yield) of 1. Anal. Calc. for C12H21Si3Cl3: C, 40.50;
H, 5.95. Found: C, 40.36; H, 5.90%. B.p. 146 °C/1 torr; MS m/z 354
(M+); 1H NMR (d CDCl3) 0.74 (s, 18H, Me2Si), 7.96 (s, 3H, phenylene
ring protons); 13C NMR (d CDCl3) 2.1 (Me2Si), 135.6, 139.4 (pheny-
lene ring carbons); 29Si NMR (d CDCl3) 20.6.
3.7. Preparation of compound 6
Compound 6 was prepared from 6.10 g (0.016 mol) of 3,
10.3 mL (0.016 mol) of a 1.58 M n-butyllithium–hexane solution,
and 6.40 g (0.016 mol) of 5 in diethyl ether, as described above.
Compound 6 (7.70 g, 73% yield) was isolated by a silica gel column
eluting with hexane–chloroform (5:1). Anal. Calc. for
C25H35Si4S4Br: C, 45.77; H, 5.38. Found: C, 45.77; H, 5.33%. M.p.
94–95 °C; MS m/z 654 (M+); 1H NMR (d CDCl3) 0.09 (s, 9H, SiMe3),
0.35 (s, 6H, SiMe2), 0.40 (s, 12H, Me2Si), 6.89 (d, 1H, J = 3.7 Hz,
thienylene proton), 6.93 (d, 1H, J = 3.7 Hz, thienylene proton),
7.02 (d, 1H, J = 3.7 Hz, thienylene proton), 7.03 (d, 1H, J = 3.7 Hz,
thienylene proton), 7.05 (d, 1H, J = 3.7 Hz, thienylene proton),
7.13 (d, 1H, J = 3.7 Hz, thienylene proton), 7.22 (d, 2H, J = 3.7 Hz,
thienylene proton); 13C NMR (d CDCl3) ꢀ2.89, ꢀ2.88, ꢀ2.84, ꢀ2.4
(Me2Si, Me3Si), 110.9, 123.8, 125.1, 125.2, 125.4, 130.6, 134.8,
135.3, 135.4, 136.9, 138.1, 138.86, 138.87, 141.6, 142.3, 142.9
(thienylene carbons); 29Si NMR (d CDCl3) ꢀ24.5, ꢀ24.4, ꢀ24.1,
ꢀ19.3.
3.4. Preparation of compound 2
In a 50 mL two-necked was placed 2.15 g (20.8 mmol) of zink
fluoride and 30 mL of THF. To this was added 2.12 g (4.73 mmol)
of 1,2,4,5-tetrakis(chlorodimethylsilyl)benzene [10]. The mixture
was heated to reflux for 5 h. After the solvent was evaporated,
the residue was distilled under reduced pressure to give 1.73 g
(96% yield) of 2. Anal. Calc. for C14H26Si4F4: C, 43.94; H, 6.85.
Found: C, 43.66; H, 6.90%. B.p. 120 °C/1 torr; MS m/z 382 (M+);
3
1H NMR (d CDCl3) 0.52 (d, 24H, Me2Si, JHF = 9.0 Hz), 7.91 (s, 2H,
phenylene ring protons); 13C NMR (d CDCl3) 0.37 (d, Me2Si,
2JHF = 19.0 Hz), 138.1 (phenylene ring carbons), 143.0 (d, pheny-
2
lene ring carbons, JHF = 14.0 Hz); 29Si NMR (d CDCl3) 21.7 (d,
3.8. Preparation of compound 8
1
SiMe2, JSiF = 279 Hz).
Compound 8 was prepared from 4.08 g (6.22 mmol) of 6, 4.0 mL
(6.32 mmol) of a 1.58 M n-butyllithium–hexane solution, and
2.42 g (6.11 mmol) of 5 in diethyl ether. Compound 8 (4.18 g,
73% yield) was isolated by a silica gel column eluting with hex-
ane–chloroform (5:1). Anal. Calc. for C37H51Si6S6Br: C, 47.45; H,
5.49. Found: C, 45.73; H, 5.30%. M.p. 151–153 °C; MS m/z 934
(M+); 1H NMR (d CDCl3) 0.10 (s, 9H, SiMe3), 0.36 (s, 6H, SiMe2),
0.41 (s, 24H, Me2Si), 6.90 (d, 1H, J = 3.7 Hz, thienylene proton),
6.94 (d, 1H, J = 3.7 Hz, thienylene proton), 7.02–7.06 (m, 5H, thien-
ylene proton), 7.14 (d, 1H, J = 3.7 Hz, thienylene proton), 7.20–7.23
(m, 4H, thienylene proton); 13C NMR (d CDCl3) ꢀ2.88, ꢀ2.87, ꢀ2.84
(3C), ꢀ2.5 (Me2Si, Me3Si), 110.9, 123.8, 125.1, 125.15, 125.24,
125.3, 125.4, 130.6, 134.8, 135.30 (2C), 135.34, 135.36, 135.37,
3.5. Preparation of compound 3
In a 500 mL three-necked flask was placed 30.00 g (0.09 mol) of
5,50-dibromo-2,20-bithiophene in 400 mL of diethyl ether. To this
was added 58.8 mL (0.09 mol) of a 1.58 M n-butyllithium–hexane
solution at ꢀ80 °C. After the mixture was stirred for 3 h at
ꢀ80 °C, it was warmed to room temperature and stirred for 12 h.
The resulting mixture was slowly added to 15.42 g (0.093 mol) of
chloropentamethyldisilane at room temperature. After the addi-
tion was completed, the solvent was removed by distillation and
hydrolyzed with dilute hydrochloric acid. The organic layer was
separated, washed with water, and dried over anhydrous magne-

A. Naka et al. / Journal of Organometallic Chemistry 694 (2009) 346–352
351
137.1, 137.5, 138.1, 138.8, 138.9, 141.7, 142.3, 142.7, 142.8, 142.9
3.12. Preparation of compound 15
(thienylene carbons); 29Si NMR (d CDCl3) ꢀ24.6, ꢀ24.5 (2Si),
ꢀ24.4, ꢀ24.1, ꢀ19.3.
Compound 15 was prepared from 3.32 g (5.06 mmol) of 6,
3.2 mL (5.06 mmol) of a 1.58 M n-butyllithium–hexane solution,
and 5.00 g (14.1 mmol) of 1. Compound 15 (2.07 g, 62% yield)
was isolated by column chromatography. Anal. Calc. for
C87H126Si15S12: C. 52.83; H, 6.42. Found: C, 52.43; H, 6.49%. M.p.
123–124 °C; MS m/z 1974 (M+); 1H NMR (d CDCl3) 0.09 (s, 27H,
SiMe3), 0.35 (s, 18H, SiMe2), 0.40 (s, 36H, SiMe2), 0.57 (s, 18H,
SiMe2), 7.02–7.04 (m, 9H, thienylene protons), 7.10 (d, 3H,
J = 3.4 Hz, thienylene protons), 7.15–7.21 (m, 12H, thienylene pro-
tons), 7.82 (s, 3H, phenylene ring protons); 13C NMR (d CDCl3) ꢀ2.8
(3C) (Me2Si), ꢀ2.4 (Me3Si), ꢀ1.3 (Me2Si), 125.1 (2C), 125.2, 125.4,
134.8, 135.3, 135.4, 135.9, 136.2, 137.1, 137.2, 137.5, 138.8,
140.5, 142.3, 142.7, 142.9, 143.1 (thienylene and phenylene ring
carbons); 29Si NMR (d CDCl3) ꢀ24.6, ꢀ24.5, ꢀ24.1, ꢀ19.3, ꢀ11.3.
3.9. Preparation of compound 10
Compound 10 was prepared from 10.87 g (0.044 mol) of 5-bro-
mo-2,20-bithiophene, a 1.58 M n-butyllithium–hexane solution,
and 17.55 g (0.02 mol) of 5. Compound 10 (18.88 g, 81% yield)
was isolated using a silica gel column eluting with a mixed solvent
of hexane–chloroform (5:1), as a colorless solid. Anal. Calc. for
C20H21Si2S4Br: C, 45.69; H, 4.03. Found: C, 45.64; H, 4.05%. M.p.
87–89 °C; MS m/z 524 (M+); 1H NMR (d CDCl3) 0.40 (br s, 12H,
SiMe2), 6.89 (d, 1H, J = 3.7 Hz, thienylene proton), 6.94 (d, 1H,
J = 3.7 Hz, thienylene proton), 6.99 (t, 1H, J = 3.7 Hz, thienylene
proton), 7.02 (d, 1H, J = 3.7 Hz, thienylene proton), 7.03 (d, 1H,
J = 3.7 Hz, thienylene proton), 7.13 (d, 1H, J = 3.7 Hz, thienylene
proton), 7.16 (d, 1H, J = 3.7 Hz, thienylene proton), 7.19 (d, 1H,
J = 5.2 Hz, thienylene proton), 7.21 (d, 1H, J = 3.7 Hz, thienylene
proton); 13C NMR (d CDCl3) ꢀ2.9 (2C) (Me2Si), 110.9, 123.8 (2C),
124.4, 125.2, 125.4, 127.8, 130.6, 135.30, 135.32, 137.2, 137.3,
138.0, 138.9, 141.7, 142.8 (thienylene carbons); 29Si NMR (d CDCl3)
ꢀ24.5, ꢀ24.3.
3.13. Preparation of compound 16
Compound 16 was prepared 2.45 g (2.62 mmol) of 8, 1.7 mL
(2.69 mmol) of a 1.58 M n-butyllithium–hexane solution, and
0.313 g (0.88 mmol) of 1. Compound 16 (0.323 g, 13% yield) was iso-
lated by column chromatography. Anal. Calc. for C123H174Si21S18: C.
52.39; H, 6.22. Found: C, 52.44; H, 6.20%. M.p. 124–125 °C; MS m/z
2814 (M+); 1H NMR (d CDCl3) 0.11 (s, 27H, SiMe3), 0.37 (s, 18H,
SiMe2), 0.41 (s, 72H, SiMe2), 0.59 (s, 18H, SiMe2), 7.03–7.06 (m,
15H, thienylene protons), 7.11 (d, 3H, J = 3.4 Hz, thienylene protons),
7.19–7.23 (m, 18H, thienylene protons), 7.84 (s, 3H, phenylene ring
protons); 13C NMR (d CDCl3) ꢀ2.84 (2C), ꢀ2.83 (2C), ꢀ2.82, ꢀ2.4,
ꢀ1.3, (Me3Si, Me2Si), 125.12, 125.13, 125.2, 125.3 (2C), 125.4,
134.8, 135.3, 135.4 (2C), 135.9, 136.2, 137.16, 137.19, 137.3, 137.4,
137.5, 138.8, 140.5 (2C), 142.3, 142.66, 142.70, 142.73, 142.9,
143.1 (thienylene and phenylene ring carbons); 29Si NMR (d CDCl3)
ꢀ24.6 (4Si), ꢀ24.1, ꢀ19.3, ꢀ11.3.
3.10. Preparation of compound 12
Compound 12 was prepared from 6.79 g (12.9 mmol) of 10,
8.2 mL (13.0 mmol) of a 1.58 M n-butyllithium–hexane solution,
and 5.11 g (12.9 mmol) of 5. Compound 12 (8.62 g, 82% yield)
was isolated using a silica gel column eluting with a mixed solvent
of hexane–chloroform (5:1), as a yellow green solid. Anal. Calc. for
C32H37Si4S6Br: C, 47.65; H, 4.63. Found: C, 47.54; H, 4.63%. M.p.
120–122 °C; MS m/z 804 (M+); 1H NMR (d CDCl3) 0.40 (br s, 24H,
SiMe2), 6.89 (d, 1H, J = 3.7 Hz, thienylene proton), 6.93 (d, 1H,
J = 3.7 Hz, thienylene proton), 6.99 (t, 1H, J = 3.7 Hz, thienylene
proton), 7.01 (d, 2H, J = 3.7 Hz, thienylene protons), 7.13 (d, 1H,
J = 3.7 Hz, thienylene proton), 7.15 (d, 2H, J = 3.7 Hz, thienylene
protons), 7.16 (d, 1H, J = 3.7 Hz, thienylene proton), 7.18 (d, 1H,
J = 5.2 Hz, thienylene proton), 7.21 (d, 3H, J = 3.7 Hz, thienylene
protons); 13C NMR (d CDCl3) ꢀ2.9 (2C), ꢀ2.84 (2C) (Me2Si), 110.9,
123.76, 123.78, 124.3, 125.19, 125.23, 125.3, 125.4, 127.8, 130.6,
135.3 (2C), 135.4 (2C), 137.1, 137.29, 137.34, 137.4, 138.0, 138.9,
141.7, 142.7, 142.76, 142.78 (thienylene carbons); 29Si NMR (d
CDCl3) ꢀ24.5 (2Si), ꢀ24.3 (2Si).
3.14. Preparation of compound 17
Compound 17 was prepared from 4.57 g (8.69 mmol) of 10,
5.5 mL (8.69 mmol) of a 1.58 M n-butyllithium–hexane solution,
and 1.02 g (2.87 mmol) of 1. Compound 17 (2.64 g, 58% yield)
was isolated by column chromatography. Anal. Calc. for
C72H84Si9S12: C. 54.49; H, 5.33. Found: C, 54.46; H, 5.28%. MS m/z
1584 (M+); 1H NMR (d CDCl3) 0.397 (s, 18H, SiMe2), 0.401 (s,
18H, SiMe2), 0.57 (s, 18H, SiMe2), 6.97 (dd, 3H, J = 5.1 Hz, 3.7 Hz,
thienylene protons), 7.01 (d, 3H, J = 3.7 Hz, thienylene protons),
7.02 (d, 3H, J = 3.7 Hz, thienylene protons), 7.09 (d, 3H, J = 3.7 Hz,
thienylene protons), 7.14 (d, 3H, J = 3.7 Hz, thienylene protons),
7.16–7.20 (m, 12H, thienylene protons), 7.81 (s, 3H, phenylene ring
protons); 13C NMR (d CDCl3) ꢀ2.9, ꢀ2.8, ꢀ1.3, 123.8, 124.3, 125.1,
125.2, 125.4, 127.8, 135.3, 135.4, 135.9, 136.2, 137.2, 137.3, 137.4,
137.5, 140.5, 142.7, 142.8, 143.1 (thienylene and phenylene ring
carbons); 29Si NMR (d CDCl3) ꢀ24.5 (2Si), ꢀ11.3.
3.11. Preparation of compound 14
In a 200 mL two-necked flask was placed 15.82 g (42.2 mmol) of
(50-bromo-2,20-bithiophen-5-yl)pentamethyldisilane 3 in 150 ml
of diethyl ether. To this was added 26.7 mL (42.2 mmol) of a
1.58 M n-butyllithium–hexane solution at ꢀ40 °C. The mixture
was added to 5.00 g (14.1 mmol) of 1 in 50 ml of ether at room
temperature. The solvent was evaporated, and the residue was
hydrolyzed with dilute hydrochloric acid. The organic layer was
separated, washed with water, and dried over anhydrous magne-
sium sulfate. Compound 14 (9.89 g, 62% yield) was isolated by col-
umn chromatography. Anal. Calc. for C51H78Si9S6: C, 53.91; H, 6.92.
Found: C, 53.51; H, 6.95%. M.p. 104–105 °C; MS m/z 1134 (M+); 1H
NMR (d CDCl3) 0.11 (s, 27H, SiMe3), 0.38 (s, 18H, SiMe2), 0.59 (s,
18H, SiMe2), 7.06 (d, 3H, J = 3.4 Hz, thienylene protons), 7.11 (d,
3H, J = 3.4 Hz, thienylene protons), 7.20 (d, 3H, J = 3.4 Hz, thienyl-
ene protons), 7.21 (d, 3H, J = 3.4 Hz, thienylene protons), 7.84 (s,
3H, phenylene ring protons); 13C NMR (d CDCl3) ꢀ2.8 (Me2Si),
ꢀ2.4 (Me3Si), ꢀ1.3 (Me2Si), 125.0, 125.3, 134.8, 135.9, 136.2,
137.0, 138.9, 140.5, 142.3, 143.2 (thienylene and phenylene ring
carbons); 29Si NMR (d CDCl3) ꢀ24.1, ꢀ19.3, ꢀ11.3.
3.15. Preparation of compound 18
Compound 18 was prepared from 4.08 g (5.06 mmol) of 12,
3.2 mL (5.06 mmol) of a 1.58 M n-butyllithium–hexane solution,
and 0.601 g (1.69 mmol) of 1. Compound 18 (1.27 g, 31% yield)
was isolated by column chromatography. Anal. Calc. for
C108H132Si15S18: C. 53.41; H, 5.48. Found: C, 53.63; H, 5.56%. M.p.
80–81 °C; MS m/z 2424 (M+); 1H NMR (d CDCl3) 0.41 (s, 72H,
SiMe2), 0.58 (s, 18H, SiMe2), 6.98 dd, 3H, J = 5.1 Hz, 3.7 Hz, thienyl-
ene protons), 7.02–7.05 (m, 12H, thienylene protons), 7.10 (d, 3H,
J = 3.7 Hz, thienylene protons), 7.16–7.22 (m, 21H, thienylene pro-
tons), 7.83 (s, 3H, phenylene ring protons); 13C NMR (d CDCl3)
ꢀ2.84 (2C), ꢀ2.83 (2C), ꢀ1.3, 123.8, 124.3, 125.1, 125.19, 125.24,

352
A. Naka et al. / Journal of Organometallic Chemistry 694 (2009) 346–352
125.3, 125.4, 127.8 (2C), 135.3, 135.4, 135.9, 136.2, 137.2, 137.285,
137.294 (2C), 137.30, 137.34, 137.46 137.50, 142.65, 142.70,
142.72, 142.3, 143.1 (thienylene and phenylene ring carbons);
29Si NMR (d CDCl3) ꢀ24.5 (4Si), ꢀ11.3.
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3.16. Preparation of compound 19
In a 100 mL two-necked flask was placed 2.66 g (5.07 mmol) of
10 in 50 mL of diethyl ether. To this suspension was added 3.3 mL
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0.42 (s, 24H, SiMe2), 6.98–7.02 (m, 8H, thienyl ring protons), 7.05
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127.7, 135.3 (2C), 135.4, 136.2, 136.6, 136.8, 137.1, 137.3, 140.2,
142.6, 142.8, 143.0 (thienylene and phenylene ring carbons); 29Si
NMR (d CDCl3) ꢀ24.4 (2Si), ꢀ9.0.
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2.5 mL (3.85 mmol) of a 1.54 M n-butyllithium–hexane solution,
and 0.301 g (0.79 mmol) of 2. Compound 20 (0.19 g, 7% yield)
was isolated by column chromatography. Anal. Calc. for
C142H174Si20S24: C. 53.10; H, 5.46. Found: C, 53.33; H, 5.10%. MS
m/z 3206 (M+); 1H NMR (d CDCl3) 0.41 (br s, 96H, SiMe2), 0.51 (s,
24H, SiMe2), 6.96 (d, 4H, J = 3.4 Hz, thienylene protons), 6.98–
7.00 (m, 4H, thienylene protons), 7.01–7.04 (m, 16H, thienyl ring
protons), 7.14 (d, 4H, J = 3.4 Hz, thienylene protons), 7.15–7.19
(m, 12H, thienylene protons), 7.21 (d, 12H, J = 3.4 Hz, thienylene
protons), 8.06 (s, 2H, phenylene ring protons); 13C NMR (d CDCl3)
ꢀ2.85, ꢀ2.83, ꢀ2.81 (2C), 1.5 (Me2Si), 123.8, 124.3, 125.1, 125.2,
125.26 (2C), 125.28 (2C), 125.4, 127.8, 135.3, 135.4 (3C), 136.4,
137.3, 137.35, 137.37 (2C), 137.39, 139.00, 142.7, 142.75, 142.77,
143.01, 143.04 (thienylene and phenylene ring carbons); 29Si
NMR (d CDCl3) ꢀ24.5 (4Si), ꢀ9.8.
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Acknowledgments
We express our appreciation to Sumitomo Chemical Co., Ltd. for
financial support. We also thank Shin-Etsu Chemical Co., Ltd. for
the gift of chlorosilanes.