Silole-containing poly(silylenevinylene)s: Synthesis, characterization, aggregation-enhanced emission, and explosive detection

Article abstract of DOI:10.1002/pola.26006

Hydrosilylation polymerizations of 1,1-dimethyl-2,5-bis(4-ethynylphenyl)-3, 4-diphenylsilole with aromatic silylhydrides including 1,4-bis(dimethylsilyl) benzene, 4,4'-bis(dimethylsilyl)biphenyl, 2,5-bis(dimethylsilyl)thiophene, and 2,7-bis(dimethylsilyl)-9,9-dihexylfluorene in the presence of Rh(PPh ₃)₃Cl catalyst in refluxed tetrahydrofuran afford a series of silole-containing poly(silylenevinylene)s. Under optimum condition, the alkyne polyhydrosilylation reactions progress efficiently and regioselectively, yielding polymers with high molecular weights (M_w up to 95,300) and good stereoregularity (E content close to 99%) in high yields (up to 92%). The polymers are processable and thermally stable, with high decomposition temperatures in the range of 420-449 °C corresponding to 5% weight loss. They are weakly fluorescent in the solution state but become emissive in the aggregate and film states, demonstrating their aggregation-enhanced emission characteristics. The explosive sensing capabilities of the polymers are examined in both solution and aggregate states. The emissions of the polymers aggregates in aqueous mixture are quenched more efficiently by picric acid in an exponential pattern with high quenching constants (up to 27,949 L mol ^-1), suggesting that the polymers aggregates are sensitive chemosensors for explosive detection. 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 A series of silole-containing poly(silylenevinylene)s are synthesized regioselectively in high yields. These polymers show aggregation-enhanced emission and sensitive response to explosives in aqueous media. Copyright

Full text of DOI:10.1002/pola.26006

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ARTICLE
Silole-Containing Poly(silylenevinylene)s: Synthesis, Characterization,
Aggregation-Enhanced Emission, and Explosive Detection
1
1,2
1
1
1
1
Zujin Zhao, Tao Jiang, Yanju Guo, Liyuan Ding, Bairong He, Zhengfeng Chang,
2
2
2
3
4
1,4
Jacky W. Y. Lam, Jianzhao Liu, Carrie Y. K. Chan, Ping Lu, Liwen Xu, Huayu Qiu,
2
Ben Zhong Tang
1
College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 310036, China
2
Department of Chemistry and State Key Laboratory of Molecular Neuroscience, The Hong Kong University of Science and
Technology, Clear Water Bay, Kowloon, Hong Kong, China
3
State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun 130012, China
4
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University,
Hangzhou 310012, China
Correspondence to: H. Y. Qiu (E-mail: huayuqiu@gmail.com) or B. Z. Tang (E-mail: tangbenz@ust.hk)
Received 3 January 2012; accepted 9 February 2012; published online 13 March 2012
DOI: 10.1002/pola.26006
ABSTRACT: Hydrosilylation polymerizations of 1,1-dimethyl-2,5-
cent in the solution state but become emissive in the aggre-
gate and film states, demonstrating their aggregation-
enhanced emission characteristics. The explosive sensing
capabilities of the polymers are examined in both solution
and aggregate states. The emissions of the polymers aggre-
gates in aqueous mixture are quenched more efficiently by
picric acid in an exponential pattern with high quenching
bis(4-ethynylphenyl)-3,4-diphenylsilole with aromatic silylhy-
0
drides including 1,4-bis(dimethylsilyl)benzene, 4,4 -bis(dime-
thylsilyl)biphenyl, 2,5-bis(dimethylsilyl)thiophene, and 2,7-
bis(dimethylsilyl)-9,9-dihexylfluorene in the presence of
3 3
Rh(PPh ) Cl catalyst in refluxed tetrahydrofuran afford a series
of silole-containing poly(silylenevinylene)s. Under optimum
condition, the alkyne polyhydrosilylation reactions progress
efficiently and regioselectively, yielding polymers with high
ꢀ1
constants (up to 27,949 L mol ), suggesting that the poly-
mers aggregates are sensitive chemosensors for explosive
detection. VC 2012 Wiley Periodicals, Inc. J Polym Sci Part A:
molecular weights (M
w
up to 95,300) and good stereoregu-
larity (E content close to 99%) in high yields (up to 92%). The
Polym Chem 50: 2265–2274, 2012
polymers are processable and thermally stable, with high
ꢁ
decomposition temperatures in the range of 420ꢀ449
C
KEYWORDS: aggregation-enhanced emission; explosive detec-
corresponding to 5% weight loss. They are weakly fluores-
tion; fluorescence; heteroatom-containing polymers; synthesis
INTRODUCTION Siloles (silacyclopentadienes) are a group of
silicon-containing five-membered cyclic dienes, which have
attracted considerable research interests due to their unique
electronic properties and potential high-technological appli-
cations. The effective interactions of the r* orbital of the
exocyclic bonds on the silicon atom and the p* orbital of the
butadiene moiety result in low-lying lowest unoccupied mo-
lecular orbital of siloles, and thus endow them with high
applications in electron transport and/or light-emitting
4
5
6
materials,
chemosensors.
solar cells,
fluorescent bioprobes,
and
7
Currently, many efforts are made to create efficient func-
tional materials for the rapid detection of nitroaromatic
explosives, such as trinitrotoluene (TNT) and 2,4,6-trinitro-
phenol (picric acid, PA), which is of significant importance
concerning the increasingly serious public security threats
and environmental pollution problems across the globe. Flu-
orescent-conjugated polymers (FCP) have been introduced as
low cost, robust materials for the detection of explosives
1
electron acceptability and fast electron mobility. Recently,
researchers found that a series of substituted propeller-like
siloles that are nonfluorescent in solutions fluoresce strongly
in aggregates or in solid films. Such a novel phenomenon
8
vapors and particles. Swager et al. demonstrated that FCPs
2
,3
coined as aggregation-induced emission (AIE)
is exactly
are superior in explosive detections to low-molecular-weight
9
opposite to the emission behaviors of most conventional
dyes, whose emissions become weak by aggregation forma-
tion. All these intriguing features have enabled siloles to find
compounds. The fast exciton migration along the conjugated
backbones provides an amplifying response to analytes, for
the interaction of an analyte molecule at any position along
Additional Supporting Information may be found in the online version of this article.
2012 Wiley Periodicals, Inc.
V
C
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1
5
the polymer chain is communicated throughout the conjuga-
tion system. However, the aggregation of the polymer back-
bones built with conventional chromophores often quenches
the light emission, and thus undermines the sensing
performance.
ature method.
The aromatic silylhydrides 1ꢀ4 were
1
6
prepared by a modified method according to literature.
1,1-Dimethyl-2,5-bis(4-ethynylphenyl)-3,4-diphenylsilole
was synthesized by our published method. IR spectra
were recorded on a Perkin-Elmer 16 PC FTIR spectropho-
1
0(g)
(5)
1
13
tometer. H and C NMR spectra were measured on a
Bruker ARX 400 spectrometer using chloroform-d as solvent
and tetramethylsilane (TMS; d ¼ 0 ppm) as internal stand-
ard. Agilent 5975 apparatus (EI, 70 eV) was used to obtain
mass spectra. Thermogravimetric analysis (TGA) was carried
on a TA TGA Netzsch TG209 under dry nitrogen at a heating
rate of 10 C min . UV–vis absorption spectra were meas-
ured on a Varian CARY 100 Bio spectrophotometer. Photolu-
minescence (PL) spectra were recorded on a Perkin-Elmer
In an effort to create polymeric fluorescent chemosensors
that can function efficiently in the aggregate state, we intro-
duced AIE units, such as silole and tetraphenylethene (TPE)
into the linear and hyperbranched polymers by metathesis,
click, coupling, and cyclotrimerization polymerizations using
1
0
acetylenes as building blocks. All of these polymers pos-
sess good solubility in common organic solvents and enjoy
high thermal stability. The results show that incorporation of
AIE-active monomers into polymers can solve the problem of
such notorious aggregation-caused quenching (ACQ). The
aggregates of the polymers containing AIE units emit more
efficiently than individually dispersive species in the solution
state. They outperform fluorescent polymers constructed by
conventional chromophores in explosive detection. A super-
amplification effect is usually observed from aggregates of
AIE-active polymers: the quenching efficiency is greatly
increased in a nonlinear fashion with increasing quencher
ꢁ
ꢀ1
LS 55 spectrofluorometer. Weight (M
w
) and number-average
(
M ) molecular weights and polydispersity indices (M /M )
n
w
n
of the polymers were estimated by a Waters Associate’s gel
permeation chromatography (GPC) system equipped with
refractive index and UV detectors. A set of monodisperse
polystyrene standards covering molecular weight range of
3
7
1
0 ꢀ10 was used for the molecular weight calibration. THF
ꢀ1
was used as eluent at a flow rate of 1.0 mL min
.
1
0(g),11
concentration.
Hydrosilylation reactions between alkynes and silylhydrides
catalyzed by various transition metals are well-established
Monomer Syntheses
1
0(g)
Silole diyne 5
was synthesized according to our pub-
1
2
approaches to construct vinyl silane derivatives. The reac-
tions have been exploited in the preparation of linear and
hyperbranched poly(silylenevinylene)s bearing functional
groups as well. The polymers with silicon atoms may exhibit
unique r*ꢀp delocalization along the polymer backbone due
to the interaction of the r* orbitals of the silicon atoms and
lished method, whereas compounds 1ꢀ4 were prepared
according to the synthetic routes shown in Scheme 2. Typical
experimental procedures for their syntheses are shown
below.
1
3
the p orbitals of the carbon–vinylene bonds. These poly-
mers show potential applications as photoresists, cross-lika-
ble prepolymers, ceramic precursors, electron-transporting
materials, optoelectronic materials, and particularly, fluores-
cent chemosensors. Trogler et al. introduced siloles through
the 1,1-postions of the metalole ring into a series of silyl–
vinyl polymers by facile hydrosilylation polymerization of
Synthesis of 1,4-Bis(dimethylsilyl)benzene (1)
To a solution of 1,4-dibromophenzene (0.47 g, 2 mmol) in
ꢁ
ether (50 mL) at ꢀ78 C, tetramethyl ethylenediamine
(TMEDA; 1.2 mL, 8 mmol) and n-butyllithium (1.6 M solu-
tion in hexane, 5 mL, 9 mmol) were added dropwise. The
ꢁ
mixture was stirred at ꢀ78 C for 1 h, and warmed to room
temperature. After stirring for 1 h, the mixture was cooled
2,3,4,5-tetraphenylsiloles with diynes. Their emissive nanoag-
ꢁ
to ꢀ78 C again, to which chlorodimethylsilane (0.8 mL, 8
gregates have shown promising application for the detection
mmol) was added dropwise. After stirring for 30 min at ꢀ78
1
4
of a wide range of explosive particles. To further explore
efficient polymeric organosilicon materials for explosive
detection, in this article, we wish to report a series of silole-
containing r*ꢀp-conjugated polymers, which are synthesized
by hydrosilylation polymerizations of 2,5-bis(4-ethynyl-
phenyl)-1,1-dimethyl-3,4-diphenylsilole with various aro-
matic silylhydrides. Their photophysical properties and appli-
cations for the explosive detection are presented.
ꢁ
C, the mixture was allowed to warm to room temperature
and kept stirring overnight. The mixture was then poured
into water and extracted with dichloromethane (DCM) by
three times. The combined organic layers were dried over
magnesium sulfate. After filtration, the solvent was evapo-
rated by rotary evaporator. The residue was purified by col-
umn chromatography (silica gel, hexane) to give 1,4-bis(di-
methylsilyl)benzene (1) (0.23 g, 56% yield) as colorless
liquid.
EXPERIMENTAL
ꢀ
1
IR (film), u (cm ): 2120 (SiAH stretching), 1250 (SiACH3
Materials and Instrumentations
1
bending), 1136 (SiAPh stretching). H NMR (400 MHz,
Tetrahydrofuran (THF) was distilled under normal pressure
from sodium benzophenone ketyl under nitrogen immedi-
ately before use. All the solvents of high purities were used
without further purification. All the chemicals were pur-
chased from Aldrich and used as received. Chlorotris(triphe-
nylphosphine)rhodium(I) was synthesized following the liter-
CDCl
3
), d (TMS, ppm): 7.57 (s, 4H), 4.43ꢀ4.47 (m, 2H), 0.37
13
(
d, 12H, J ¼ 3.6 Hz). C NMR (100 MHz, CDCl ), d (TMS,
3
þ
ppm): 138.6, 133.6, ꢀ3.7. MS (EI): 193 (M ꢀ 1).
Other aromatic silylhydrides were prepared by a similar pro-
cedure and their characterization data are given below.
2
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0
1
4
,4 -Bis(dimethylsilyl)biphenyl (2)
bending), 1114 (SiAPh stretching). H NMR (400 MHz,
CDCl ), d (TMS, ppm): 7.63–7.56 (Ar-H), 7.23–7.21 (Ar-H),
ꢀ
1
Colorless liquid, yield 48%. IR (film), u (cm ): 2118 (SiAH
3
stretching), 1250 (SiACH bending), 1117 (SiAPh stretch-
7.01–6.78 (Ar-H and E-ArCH ¼¼ ), 6.50 (E-SiCH ¼¼ ), 0.46–0.42
3
1
13
ing). H NMR (400 MHz, CDCl ), d (TMS, ppm): 7.67ꢀ7.62
[Si(CH ) ]. C NMR (100 MHz, CDCl ), d (TMS, ppm): 154.2,
3
3 2
3
1
3
(
m, 8H), 4.52ꢀ4.48 (m, 2H), 0.41 (d, 12H, J ¼ 3.6 Hz).
C
145.2, 141.7, 138.8, 135.3, 134.4, 130.0, 129.2, 128.8, 127.5,
126.6, 126.3, 126.0, ꢀ2.4, ꢀ3.7.
NMR (100 MHz, CDCl ), d (TMS, ppm): 142.0, 136.5, 134.8,
3
þ
1
26.8, ꢀ3.5. MS (EI): 270 (M ).
P3/5
2
,5-Bis(dimethylsilyl)thiophene (3)
ꢀ
1
Yellowish powder, yield 85%. M 30,800; M /M 2.8 (GPC,
w w n
Colorless liquid, yield 51%. IR (film), u (cm ): 2127 (SiAH
ꢀ
1
polystyrene calibration). IR (KBr), u (cm ): 1249 (SiACH3
stretching), 1250 (SiACH bending), 1013 (SiAPh stretch-
3
1
1
bending), 1008 (SiAAr stretching). H NMR (400 MHz,
ing). H NMR (400 MHz, CDCl ), d (TMS, ppm): 7.40 (s, 2H),
3
1
3
CDCl
3
), d (TMS, ppm): 7.34 (Ar-H), 7.22–7.20 (Ar-H), 7.00–
4
.63ꢀ4.59 (m, 2H), 0.42 (d, 12H, J ¼ 4.0 Hz). C NMR (100
6
.76 (Ar-H and E-ArCH ¼¼ ), 6.47 (E-SiCH ¼¼ ), 0.46–0.44
MHz, CDCl ), d (TMS, ppm): 135.8, 125.8, ꢀ2.6. MS (EI): 200
3
13
þ
[Si(CH
) ]. C NMR (100 MHz, CDCl ), d (TMS, ppm): 154.2,
3 2 3
(
M ).
145.2, 144.4, 141.5, 140.0, 138.8, 135.9, 135.2, 128.7, 128.4,
2
,7-Bis(dimethylsilyl)-9,9-dihexylfluorene (4)
128.0, 127.5, 126.6, 125.7, ꢀ1.2, ꢀ3.6.
ꢀ
1
Colorless liquid, yield 56%. IR (film), u (cm ): 2118 (SiAH
stretching), 1248 (SiACH bending), 1092 (SiAPh stretch-
ing). H NMR (400 MHz, CDCl ), d (TMS, ppm): 7.71 (d, 2H, J
3
P4/5
1
3
Yellowish powder, yield 82%. Mw 14,900; M /M 1.8 (GPC,
w n
polystyrene calibration). IR (KBr), u (cm ): 1247 (SiACH3
bending), 1091 (SiAAr stretching). H NMR (400 MHz,
ꢀ
1
¼
7.6 Hz), 7.51 (d, 4H, J ¼ 6.4 Hz), 4.53ꢀ4.49 (m, 2H),
1
1
3
1
2
.99ꢀ1.95 (m, 4H), 1.07ꢀ0.65 (m, 30H), 0.45 (d, 12H, J ¼
1
3
.6 Hz). C NMR (100 MHz, CDCl ), d (TMS, ppm): 150.2,
42.1, 136.2, 132.5, 128.4, 119.3, 55.0, 40.1, 31.8, 29.9, 29.2,
9.1, 23.7, 22.7, 14.1, ꢀ3.4. MS (EI): 506 (M ).
3
CDCl ), d (TMS, ppm): 7.67 (Ar-H), 7.48 (Ar-H), 7.21–7.19
3
(
Ar-H), 7.00–6.78 (Ar-H and E-ArCH ¼¼ ), 6.53 (E-SiCH ¼¼ ), 1.93
þ
13
[
C(CH )], 1.25–0.62 [(CH ) CH ], 0.45–0.42 [Si(CH ) ].
C
2
2 6
3
3 2
NMR (100 MHz, CDCl ), d (TMS, ppm): 154.2, 150.2, 145.0,
3
Polymerization
1
1
4
41.9, 141.5, 139.9, 138.8, 137.1, 135.4, 132.5, 129.9, 129.1,
28.6, 128.2, 127.5, 126.7, 126.5, 126.3, 126.2, 119.2, 54.9,
0.0, 31.8, 29.9, 29.2, 29.1, 23.8, 22.6, 14.1, ꢀ2.2, ꢀ3.7.
All the polymerization reactions and manipulations were car-
ried out under nitrogen, except for the purification of the
polymers, which was done in open air. A typical experimen-
tal procedure for the polymerization of silole diyne 5 with 1
is given below as an example. Into a baked 25-mL flask,
silole diyne 5 (46.3 mg, 0.1 mmol), 1,4-bis(dimethylsilyl)ben-
zene (1) (20 mg, 0.1 mmol), and Rh(PPh ) Cl (1.3 mg,
RESULTS AND DISCUSSION
Monomer Syntheses
3
3
Since the first observation of novel AIE phenomenon from 1-
0.0014 mmol) were added. The flask was evacuated under
2(a)
methyl-1,2,3,4,5-pentaphenylsilole,
we have been working
vacuum for half an hour and then flushed with nitrogen.
Freshly distilled THF (2 mL) was injected into the flask to
dissolve the monomers. After refluxing for 12 h under nitro-
gen, the solution was then cooled to room temperature and
was added into ethanol (150 mL) through a cotton filter
under stirring. The precipitates were collected and dissolved
in THF (3 mL) and were precipitated from ethanol for two
more times. After filtration, the polymer was dried in vac-
on design and syntheses of new silole molecules with spe-
cific chemical structures and functionalities. The endeavors
have enabled us to get various silole derivatives with poten-
tial applications in materials science and biological process,
and have better understanding on the structure–property
relationships of silole-based materials. 2,5-Bis(4-ethynyl-
phenyl)-1,1-dimethyl-3,4-diphenylsilole (5) is an interesting
silole derivative bearing two acetylene groups at the periph-
ꢁ
uum oven at 40 C to a constant weight. The polymer P1/5
ery, which has been used to build hyperbranched polymer
was obtained as yellowish powder in 92% yield. M
/M 2.8 (GPC, polystyrene calibration).
w
95,300;
10(g)
through cyclotrimerization polymerization.
In this work,
M
w
n
we use silole derivative as one of the monomers for the
hydrosilylation polymerization. Scheme 1 illustrates the syn-
thetic route to 5, and the detailed procedures had been pre-
ꢀ
1
IR (KBr), u (cm ): 1248 (SiACH
3
bending), 1133 (SiAPh
1
stretching). H NMR (400 MHz, CDCl ) d (TMS, ppm): 7.52
3
1
0(g)
(
Ar-H), 7.19 (Ar-H), 7.00–6.78 (Ar-H and E-ArCH ¼¼ ), 6.47 (E-
sented in our previous publication.
On the other hand,
1
3
SiCH ¼¼ ), 0.46–0.38 [Si(CH ) ]. C NMR (100 MHz, CDCl ), d
we designed a group of aromatic silylhydrides (1ꢀ4), whose
synthetic routes are shown in Scheme 2. These aromatic
silylhydrides were successfully prepared in moderate yields
of (48ꢀ56%) by lithiation of aryl bromide with n-butyl-
lithium in the presence of TMEDA, and followed treatment
with chlorodimethylsilane. The addition of TMEDA was help-
ful to stabilize the lithiated intermediates, and thus increase
reactions yields. All the structures of the monomers were
confirmed by standard spectroscopic methods with satisfac-
tory data.
3
2
3
(
1
ꢀ
TMS, ppm): 154.2, 145.1, 141.1, 139.9, 139.5, 138.8, 135.3,
33.2, 129.9, 129.1, 128.7, 127.5, 126.5, 126.3, 126.2, 126.1,
2.6, ꢀ3.6.
Other polymers were prepared by a similar procedure and
their characterization data are given below.
P2/5
Yellowish powder, yield 90%. Mw 23,000; M /M 3.0 (GPC,
w
n
ꢀ
1
polystyrene calibration). IR (KBr), u (cm ): 1249 (SiACH3
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SCHEME 1 Syntheses of silole diyne 5 and its hydrosilylation polymerization with aromatic silylhydrides.
Polymerization
Hydrosilylations of alkynes are commonly catalyzed by tran-
sition mental catalysts, such as Rh(PPh ) Cl, H PtCl , Kar-
stedt’s catalyst, and so forth. Our previous works showed
that the alkyne polyhydrosilylations underwent regioselec-
tively in the presence of rhodium catalyst [Rh(PPh ) Cl] in
moderate yields (55.9ꢀ78.1%). Herein, the Rh(PPh ) Cl
polymerization. Under optimum conditions, polymers P1/
5ꢀP4/5 with high molecule weights (14,900–95,300) were
synthesized in high yields in (82ꢀ92%). All the polymers
are readily soluble in common organic solvents, such as THF,
toluene, DCM, and chloroform, which are partially attributed
3
3
2
6
3
to the flexible sp hybridized silicon bridges.
3
3
1
7
3
3
was also used to catalyze polymerization reactions of these
new monomers. To further increase reaction yields and get
high molecular weights, the polymerization conditions
including solvents, concentration, time, and the amounts of
the catalyst were investigated using the polymerization of 1
and 5 as an example. As can be seen in Table 1, reaction
yields and molecular weights became higher by prolonging
reaction time gradually from 4 to 12 h. Lowering the fraction
Structural Characterization
The structures of new polymeric products were character-
ized by IR and NMR spectroscopies and satisfactory analysis
data corresponding to their expected molecular structures
were obtained. An IR spectrum of P1/5 is shown in Figure 1
TABLE 1 Syntheses of Silole-Containing
a
Poly(silylenevinylene)s
(
mol %) of catalyst from 1.4 to 0.5% relative to monomer
decreased reaction yields slightly but caused notable detri-
mental effect to the molecular weight. The effects of the
monomers concentrations were also tested. Reaction with a
moderate monomer concentration of 0.1 mM showed higher
yields and higher molecular weights than those with doubled
or halved concentrations. Moreover, the reaction carried out
in THF offered better results than in toluene, suggesting that
the polar solvents were more suitable for the hydrosilylation
Solvent
Catalyst Time
w
M / Yield
b
w
b
No. Polymer ([1ꢀ5], M) (mM)
(h)
M
M
n
(%)
1
2
3
4
5
6
7
8
P1/5
P1/5
P1/5
P1/5
P1/5
P1/5
P1/5
P1/5
THF (0.05) 0.7
THF (0.05) 0.7
THF (0.05) 0.7
THF (0.05) 0.55
THF (0.05) 0.25
4
8
27,800 4.0 82
48,400 4.5 89
95,300 2.8 92
74,800 4.0 91
34,500 2.9 88
36,800 4.6 89
13,500 2.4 75
23,500 3.4 87
12
12
12
12
12
12
THF (0.1)
THF (0.025) 0.275
Toluene 0.55
0.05)
1.1
(
9
1
1
1
1
1
a
P2/5
P2/5
P3/5
P3/5
P4/5
P4/5
THF (0.05) 0.55
THF (0.05) 0.7
THF (0.05) 0.55
THF (0.05) 0.7
THF (0.05) 0.55
THF (0.05) 0.7
12
12
12
12
12
12
14,300 2.3 83
23,000 3.0 90
25,300 3.3 82
30,800 2.8 85
12,600 2.1 84
14,900 1.8 82
0
1
2
3
4
3 3
Carried out in refluxed THF under nitrogen using Rh(PPh ) Cl as cata-
lyst. For the reaction using toluene as solvent, temperature was kept at
ꢁ
7
b
0
C. Concentration: [1ꢀ4] ¼ [5].
SCHEME 2 Syntheses of aromatic silylhydrides.
Determined by GPC in THF on the basis of a polystyrene calibration.
2
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becomes broader and stronger after the polymerization,
revealing that the triple bonds in 5 and the dimethylsilyl
groups in 1 have been transformed into vinyl silylene units
in P1/5. Similar features are also observed from the IR spec-
tra of P2/5ꢀP4/5.
The NMR analyses are also carried out to confirm the poly-
mer structures, the results from which agree with above
1
observations. Figure 2 shows the H NMR spectra of P1/5
and monomers 1 and 5 in chloroform-d. The acetylene and
SiAH proton resonances of 5 and 1 at d 3.05 and 4.45,
respectively, are disappeared in the NMR spectrum of P1/5.
Meanwhile, new peaks at d 6.47 and 6.81 are found, which
are assigned to the proton absorptions of the linear E-vinyl-
1
7
ene structure, but the associated absorptions of the Z-vi-
nylene protons around d 6.00 are hardly discernible, suggest-
3 3
ing that the hydrosilylation catalyzed by Rh(PPh ) Cl is
regioselective, which is in accordance with our previous find-
ings. No unexpected peaks are found, and all the peaks can
FIGURE 1 IR spectra of (A) 5, (B) 1, and (C) P1/5.
17
be readily assigned. Thus, the polymeric product is indeed
P1/5 with a regular molecular structure as shown in Scheme
1. Similar observations were found in the spectra of P2/
5ꢀP4/5 with dominative E contents. The structures of the
as an example. The spectra of monomers 1 and 5 are also
given in the same figure for the sake of comparison. The
BCAH and CBC stretching vibrations of 5 occur at 3286
ꢀ
1
13
and 2104 cm , respectively, which are not observed in P1/
polymer were further investigated by C NMR analysis. The
1
3
5
. The IR spectrum of 1 shows SiAH stretching vibration at
C NMR spectra of P1/5, 1, and 5 are shown in Figure 3.
ꢀ
1
2120 cm , which is absent in P1/5. While the SiACH
The acetylene carbon atoms of 5 resonate at d 84.0 and 77.3
but similar peaks are absent in the spectra of P1/5ꢀP4/5,
indicating that most acetylene units have reacted with dime-
thylsilyl groups.
3
ꢀ
1
bending vibration at 1250 cm derived from monomer 1 is
discernible in the IR spectrum of P1/5. Moreover, the peak
ꢀ
1
around 1600 cm associated with C ¼¼ C stretching vibration
Thermal Stability
The thermal stabilities of these silole-containing polymers
were evaluated by TGA. As shown in Figure 4, all the
1
13
FIGURE 3 C NMR spectra of (A) 5, (B) 1, and (C) P1/5 in chlo-
FIGURE 2 H NMR spectra of (A) 5, (B) 1, and (C) P1/5 in chlo-
roform-d.
roform-d.
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FIGURE 6 PL spectra of P1/5ꢀP4/5 in dilute THF solutions
10 lM).
FIGURE 4 TGA thermograms of P1/5ꢀP4/5 recorded under
(
ꢁ
ꢀ1
.
nitrogen at a heating rate of 10 C min
5
ꢀP4/5 show similar absorption spectra with absorption
polymers are thermally stable. The P1/5ꢀP3/5 lose 5% of
maxima in the range of 380ꢀ384 nm. Similarly, P1/5ꢀP4/5
show close PL at ꢂ506 nm (Fig. 6). However, the emissions
of P1/5ꢀP4/5 are quite weak when molecularly dissolved
in dilute THF solutions (10 lM). Their fluorescence quantum
ꢁ
their weights (T ) at 441ꢀ449 C (Table 1), which are higher
d
ꢁ
than that of P4/5 (420 C). The higher T
d
s of P1/5ꢀP3/5
are understandable because they are constructed mainly
from aromatic rings without long alkyl chains, which possess
a high resistance to thermolysis. Moreover, P1/5ꢀP3/5
remain about 60% weight even at temperatures up to 750
yields (U ) measured using 9,10-diphenylanthracene as
F
standard are rather low (0.99ꢀ1.44%, Table 2), which are
1
8
much lower than those of biphenyl, fluorene, and their
polymeric derivatives. Similar phenomena are also observed
when covalently connecting conventional chromophores (py-
rene, anthracene, fluorene, carbazole, etc.) with AIE lumino-
ꢁ
C, which is attributive to their high silicon contents and/or
possible crosslinking reaction. Such good thermal properties
reveal their potential utility as ceramic precursors.
1
9
gens (TPE and silole) in our previous works. The intramo-
lecular rotations (IMR) of the phenyl blades attached at the
silole stator have effectively consumed the excited state
energy of the polymers, rendering quite weak emission in
the solution state. These polymers become emissive when
fabricated as thin solid films. The films of P1/5ꢀP4/5 show
Optical Property
Figure 5 shows the absorption spectra of the silole-contain-
ing poly(silylenevinylene)s in their dilute THF solutions. P1/
TABLE 2 Optical and Thermal Properties and Quenching
a
Constants of Silole-Containing Poly(silylenevinylene)s
k
abs
(
nm)
k
em (nm)
F
U (%)
T
d
K
b
c
ꢁ
ꢀ1
Soln Soln Aggr Film Soln
Film ( C) (L mol
)
P1/5 383
P2/5 384
P3/5 380
P4/5 381
a
507
506
505
507
512
512
511
506
528 0.99
519 1.19
520 1.44
533 1.25
7.7
22.0
10.6
11.6
442
6,220
441 27,368
449 20,107
420 27,949
Abbreviation: soln, dilute THF solution; aggr, aggregates in aqueous
mixture; film, drop-casted film on quartz; T , decomposition tempera-
d
ture for 5% weight loss; kabs, absorption maximum in THF solution; kem
,
emission maximum.
b
Fluorescence quantum yield in THF solution measured using 9,10-
diphenylanthracene as standard (U
c
F
¼ 90% in cyclohexane).
FIGURE 5 Absorption spectra of P1/5ꢀP4/5 in dilute THF solu-
tions (10 lM).
Fluorescence quantum yield of the solid film measured by an cali-
brated integrating sphere.
2
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P4/5 in THF/water mixture as an example. As indicated in
the figure, the emission intensity enhanced gradually with
the increase of f . This is because that addition of a large
w
amount of water into the THF solution of polymer P4/5
causes its molecules to aggregate, due to the immiscibility of
the hydrophobic polymer with the hydrophilic medium. The
aggregate formation restricts the IMR, and thus blocks the
channel of nonradiative decay, changing the polymer to a
strong emitter. Clearly, polymer P4/5 is AEE active. It is AEE
active because the emission of the polymer in the solution
state is not completely quenched by IMR process of phenyl
2
,3
blades of siloles. In the polymer systems, the silole units
are covalently embedded in the conjugated polymer back-
bone, and meantime, polymer chains may adopt entangled
conformations, both of which have inhibited the IMR process
in some extent and thus reduced nonradiative energy decay.
This is different from its AIE-active silole monomer, whose
light emission in solution is severely extinguished by IMR
process. The AEE effect is not an isolated case observed in
P4/5, and P1/5ꢀP3/5 exhibit similar emission enhancement
behaviors (Supporting Information Figs. S1–S3).
FIGURE 7 PL spectra of P1/5ꢀP4/5 in film state.
green emission peaked at 519ꢀ533 nm (Fig. 7), which are
bathochromically shifted compared with those in solutions.
This can be interpreted as caused by active intermolecular
interactions between aromatic rings in the condensed phase.
Explosive Detection
Rapid detection of explosives is greatly demanded in an
effort to better combat terrorism and control environmental
pollution. The success in the detection of explosives using
AIE- or AEE-active small molecules and polymers encourages
us to explore the utility as chemosensors of these new silole-
containing poly(silylenevinylene)s. With this in mind, we
monitor the PL changes of polymers in both solution and ag-
gregate states in the presence of PA. PA is used as a model
compound for it is commercially available and widely used
in the manufacture of rocket fuels, fireworks, matches, and
Much higher U values (7.7ꢀ22.0%) than those in solutions
F
are measured from the polymers films by a calibrated inte-
grating sphere, which are comparable with those of reported
1
0(g),17
silole- or TPE-based polymers.
The greatly enhanced
emission efficiencies of the polymers in the solid state sug-
gest that they are of aggregation-enhanced emission (AEE)
characteristics.
2
0
To further confirm the AEE characteristics of these silole-
containing poly(silylenevinylene)s, we measured their PL
spectra in THF/water mixtures with different water fractions
so forth, whose explosive power is somewhat superior to
that of TNT. Figure 9(A,B) shows the PL spectra of polymer
P4/5 in THF solutions and in THF/water mixtures (fw
90%) on PA addition, respectively. In THF solution, the PA
¼
(fw vol %). Figure 8(A) displays the PL spectra of polymer
FIGURE 8 (A) PL spectra of P4/5 in THF and THF/water mixtures with different water fractions. (B) Changes in the relative PL inten-
–
5
sity (I/I
o
) with the composition of the THF/water mixture. I
o
¼ PL intensity in pure THF solution. Concentration: 10 M; excitation
wavelength: 350 nm.
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–5
FIGURE 9 Fluorescence quenching of P4/5 in (A) THF and (B) THF/water mixture (1:9 v/v) by PA. Concentration of P4/5: 10 M; ex-
citation wavelength: 350 nm. (C) Stern–Volmer plot of I ¼ PL intensity in
/I ꢀ 1 value versus [PA] in THF/water mixture (1:9 v/v). I
in THF/water mixture (1:9 v/v). Inset in panel C: fluorescence image of P4/5 de-
0
0
k[PA]
0
the absence of PA. (D) Plot of I /I value versus e
posited on a filter paper with a spot of PA solution under UV illumination.
Io
¼ Aek½PAꢃ þ B
(1)
addition causes decrease in PL intensity of P4/5 in some
extent but the light emission is not totally quenched even a
large amount of PA is added. The inferior quenching effect is
I
where A and B are constants, and k denotes the static
quenching constant. By fitting the Stern–Volmer plot shown
in Figure 9(C), eq 2 is obtained
partially due to its weak emission in the dispersive state.
The aggregates of P4/5 in THF/waters mixture (fw ¼ 90%),
however, show sensitive response to PA. The emission is
progressively weakened with increase of PA concentration
Io
10;526½PAꢃ
(
[PA]). The detection is of high sensitivity, and emission
¼ 2:60e
ꢀ 1:55
(2)
I
quenching can be clearly discerned at a [PA] as low as 1
ꢀ
1
ppm. At a [PA] of 64 lg mL , virtually no light is observed
When the [PA] is very low, eq (1) can be transformed to eq
from the 90% aqueous mixture. The Stern–Volmer plot of
(
3) using a mathematical treatment of Taylor expansion:
relative PL intensity (I /I ꢀ 1) versus [PA] gives a curve
0
bending upward [Fig. 9(C)], instead of a linear line, revealing
Io
¼
Að1 þ k½PAꢃÞ þ B ¼ Ak½PAꢃ þ A þ B ¼ K½PAꢃ þ C (3)
a
superamplification effect in the emission quenching
I
1
0(g),11
process. According to our previous findings,
it is
considered that the fluorescence annihilation of polymer
aggregates should be in a static quenching fashion that gives
nonlinear Stern–Volmer plots. The effective quenching sphere
model (eq 1) can be used to describe the quenching process
by the static mechanism.
where K ¼ kA and C ¼ A þ B ¼ 1. Therefore, the static
quenching constant or the K value of the Stern–Volmer plot
for polymer P4/5 aggregates in THF/water mixture (f
¼
w
ꢀ
1
90%) is 27,368 L mol . By plotting the relative PL intensity
k[PA]
(I
/I) versus e
o
, a linear line is obtained [Fig. 9(D)] with a
2
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ꢀ
1
k value of 10,526, which enables quantitative analysis. The
quenching constant K value is higher than those of the
reported poly(tetraphenylsilole-vinylene) and other linear
27,949 L mol , demonstrating a superamplification effect.
These results suggest that they are promising candidates for
sensitive explosive detection.
ꢀ
1 14(a),14(e)
polysiloles (<20,000 L mol ).
Similar sensing capa-
The authors acknowledge financial support from National Nat-
ural Science Foundation of China (21074028 and 21104012),
Natural Science Foundation of Zhejiang Province (Y4110331),
and the Research Grant Council of Hong Kong (HKUST2/CRF/
bilities are also observed from P1/5, P2/5, and P3/5, with K
ꢀ
1
values of 6220, 20,107, and 27,949 L mol , respectively
Supporting Information Figs. S4–S6). The K values of P2/
(
5
ꢀP4/5 are higher than that of P1/5, which is probably due
1
0 and N_HKUST620/11).
to the higher emission efficiencies in the aggregate state and
better electron-donating abilities of aromatic segments in
P2/5ꢀP4/5 that promote the potentially involved Lewis
acid–base interactions between the polymers and the PA
REFERENCES AND NOTES
1
0(g),14(e)
1 (a) Khabashesku, V. N.; Balaji, V.; Boganov, S. E.; Nefedov,
O. M.; Michl, J. J. Am. Chem. Soc. 1994, 116, 320–329; (b)
Tamao, K.; Yamaguchi, S.; Ito, Y.; Matsuzaki, Y.; Yamabe, T.;
Fukushima, M.; Macromolecules 1995, 28, 8668–8675; (c)
Tamao, K.; Ohno, S.; Yamaguchi, S. Chem. Commun. 1996,
873–1874; (d) Yamaguchi, S.; Tamao, K. J. Chem. Soc., Dalton
Trans. 1998, 3693–3702; (e) Chan, L. H.; Lee, R. H.; Hsieh, C. F.;
Yeh, H. C.; Chen, C. T. J. Am. Soc. Chem. 2002, 124,
469–6479; (f) Chan, L. H.; Yeh, H. C.; Chen, C. T. Adv. Mater.
2001, 13, 1637–1641; (g) Murata, H.; Malliaras, G. G.; Uchida,
M.; Shen, Y.; Kafafi, Z. H. Chem. Phys. Lett. 2001, 339, 161–166;
h) M a€ kinen, A. J.; Uchida, M.; Kafafi, Z. H. J. Appl. Phys. 2004,
5, 2832–2838.
analytes.
Generally, the aggregate formation of polymers composed by
the conventional ACQ chromophores weakens the light emis-
sion due to the formation of detrimental species, such as
excimers and exciplexes. Such ACQ effect is disadvantageous
to sensing performances of the polymers. While polymers
created using AIE units exhibit opposite emission behaviors.
These silole-containing polymers are emissive in aggregate
state, which is beneficial to the sensitivity of detection. More-
over, the aggregates possess numerous cavities for the
quencher molecules to entry in, offering additional inter-
1
6
(
9
1
1
2 (a) Luo, J.; Xie, Z.; Lam, J. W. Y.; Cheng, L.; Chen, H.; Qiu, C.;
Kwok, H. S.; Zhan, X.; Liu, Y.; Zhu, D.; Tang, B. Z. Chem. Com-
mun. 2001, 1740–1741; (b) Hong, Y.; Lam, J. W. Y.; Tang, B. Z.
Chem. Commun. 2009, 4332–4353; (c) Liu, J.; Lam, J. W. Y.;
Tang, B. Z. J. Inorg. Organomet. Polym. Mater. 2009, 19,
249–285; (d) Hong, Y.; Lam, J. W. Y.; Tang, B. Z. Chem. Soc.
Rev. 2011, 40, 5361–5388; (e) Qin, A.; Lam, J. W. Y.; Tang, B. Z.
Prog. Polym. Sci. 2012, 37, 182–209.
branched diffusion channels for exciton migration. There-
fore, the superquenching effect can be interpreted as a coop-
erative effect of the emission quenching by the PA molecules
binding in the inner cavities and outer surfaces through elec-
tron donor–acceptor interaction and/or energy transfer.
Since these polymers are emissive in the film state, the ex-
plosive detection that can be carried out using polymer-
coated strips is predictable. A prototype of a solid-state che-
mosensor is prepared by simply dipping a filter paper into a
polymer P4/5 solution. The emissive test paper is obtained
after solvent evaporation. The detection process is fast and
the assay procedure is simple. When a PA solution is
dropped onto the test paper, the PA-covered spot become
nonfluorescent, which is vividly discernable to the naked eye
as seen from the example shown in the inset of Figure 9(C),
under UV illumination. The results suggest that these silole-
containing poly(silylenevinylene)s are promising candidates
for portable sensitive chemosensor devices for explosive
detection.
3
(a) Li, Z.; Dong, Y.; Mi, B.; Tang, Y.; H a€ ussler, M.; Tong, H.;
Dong, Y.; Lam, J. W. Y.; Ren, Y.; Sun, H. H. Y.; Wong, K. S.;
Gao, P.; Williams, I. D.; Kwok, H. S.; Tang, B. Z. J. Phys. Chem.
B 2005, 109, 10061–10066; (b) Dong, Y.; Lam, J. W. Y.; Li, Z.;
Tong, H.; Dong, Y.; Feng, X. D.; Tang, B. Z. J. Inorg. Organo-
met. Polym. Mater. 2005, 15, 287–291; (c) Zhao, Z.; Wang, Z.;
Lu, P.; Chan, C. Y. K.; Liu, D.; Lam, J. W. Y.; Sung, H. H. Y.; Wil-
liams, I. D.; Ma, Y.; Tang, B. Z. Angew. Chem. Int. Ed. 2009, 48,
608–7611; (d) Yu, G.; Yin, S.; Liu, Y.; Chen, J.; Xu, X.; Sun, X.;
Ma, D.; Zhan, X.; Peng, Q.; Shuai, Z.; Tang, B. Z.; Zhu, D.; Fang,
W.; Luo, Y. J. Am. Chem. Soc. 2005, 127, 6335–6346.
7
4
(a) Tamao, K.; Uchida, M.; Izumizawa, T.; Fukukawa, K.;
Yamaguchi, S. J. Am. Chem. Soc. 1996, 118, 11974–11975; (b)
Uchida, M.; Izumizawa, T.; Nakano, T.; Yamaguchi, S.; Tamao,
K.; Furukawa, K. Chem. Mater. 2001, 13, 2680–2683; (c) Murata,
H.; Kafafi, Z. H.; Uchida, M. Appl. Phys. Lett. 2002, 80, 189–191;
(d) Liu, Y.; Chen, Z.; Chen, J.; Wang, F.; Cao, Y. Polym. Bull.
CONCLUSIONS
2
007, 59, 31–44; (e) Geramita, K.; McBee, J.; Shen, Y.; Radu, N.;
In summary, a series of silole-containing poly(silyleneviny-
lene)s with high molecular weights are regioselectively syn-
thesized in high yields by Rh(PPh ) Cl-catalyzed hydrosilyla-
3 3
Tilley, T. D. Chem. Mater. 2006, 18, 3261–3265; (f) Son, H.-J.;
Han, W.-S.; Chun, J.-Y.; Lee, C.-J.; Han, J.-I.; Ko, J.; Kang, S. O.
Organometallics 2007, 26, 519–526; (g) Tang, B. Z.; Zhan, X.;
Yu, G.; Lee, P. P. S.; Liu, Y.; Zhu, D. J. Mater. Chem. 2001, 11,
tion polymerization of 2,5-bis(4-ethynylphenyl)silole with
aromatic silylhydrides in refluxed THF. All the polymers are
soluble and processable. They enjoy high thermal stability
with decomposition temperatures in the range of 420ꢀ449
2
974–2978; (h) Zhao, Z.; Chen, S.; Lam, J. W. Y.; Jim, C. K. W.;
Chan, C. Y. K.; Wang, Z.; Lu, P.; Kwok, H. S.; Ma, Y.; Tang, B. Z.
J. Phys. Chem. C 2010, 114, 7963–7972; (i) Du, X.; Wang, Z. Y.
Chem. Commun. 2011, 47, 4276–4278.
ꢁ
C. The polymers are weakly fluorescent in the solution state
5
(a) Mi, B.; Dong, Y.; Li, Z.; Lam, J. W. Y.; H a€ ußler, M.; Sung,
but become strong emitters when aggregated in poor sol-
vents or fabricated as thin films, exhibiting a feature of AEE.
The emissions of the polymers aggregates are quenched
exponentially by PA with high quenching constants up to
H. H. Y.; Kwok, H. S.; Dong, Y.; Williams, I. D.; Liu, Y.; Luo, Y.;
Shuai, Z.; Zhu, D.; Tang, B. Z. Chem. Commun. 2005,
3
583–3585; (b) Wang, F.; Luo, J.; Yang, K.; Chen, J.; Huang, F.;
Cao, Y. Macromolecules 2005, 38, 2253–2260; (c) Chen, J.; Cao,
WWW.MATERIALSVIEWS.COM
JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY 2012, 50, 2265–2274
2273

JOURNAL OF
POLYMER SCIENCE
ARTICLE
WWW.POLYMERCHEMISTRY.ORG
Y. Macromol. Rapid Commun. 2007, 28, 1714–1742; (d) Hong,
Y.-R.; Wong, H.-K.; Moh, L. C. H.; Tan, H.-S.; Chen, Z.-K. Chem.
Commun. 2011, 47, 4920–4922; (e) Song, J.; Du. C.; Li, C.; Bo,
Z. J. Polym. Sci. Part A: Polym. Chem. 2011, 49, 4267–4274.
(h) Wang, J.; Mei, J.; Yuan, W.; Lu, P.; Qin, A.; Sun, J.; Ma, Y.;
Tang, B. Z. J. Mater. Chem. 2011, 21, 4056–4059; (i) Hu, R.; Mal-
donado, J. L.; Rodriguez, M.; Deng, C.; Jim, C. K. W.; Lam, J.
W. Y.; Yuen, M. M. F.; Ramos-Ortiz, G.; Tang, B. Z. J. Mater.
Chem. 2012, 22, 232–240.
6
(a) Yu, Y.; Feng, C.; Hong, Y.; Liu, J.; Chen, S.; Ng, K. M.;
Luo, K. Q.; Tang, B. Z. Adv. Mater. 2011, 23, 3298–3302; (b) Yu,
Y.; Hong, Y.; Feng, C.; Liu, J.; Lam, J. W. Y.; Faisal, M.; Ng, K.
M.; Luo, K. Q.; Tang, B. Z. Sci. China Ser. B: Chem. 2009, 52,
11 (a) Liu, J.; Zhong, Y.; Lu, P.; Hong, Y.; Lam, J. W. Y.; Faisal,
M.; Yu, Y.; Wong, K. S.; Tang, B. Z. Polym. Chem. 2010, 1,
426–429; (b) Lu, P.; Lam, J. W. Y.; Liu, J.; Jim, C. K. W.; Yuan,
W.; Xie, N.; Zhong, Y.; Hu, Q.; Wong, K. S.; Cheuk, K. K. L.;
Tang, B. Z. Macromol. Rapid Commun. 2010, 31, 834–839.
15–19; (c) Faisal, M.; Yu, Y.; Lam, J. W. Y.; Liu, J.; Zhang, B.;
Lu, P.; Zhang, X.; Tang, B. Z. Adv. Funct. Mater. 2011, 21,
1
733–1740.
1
2 (a) Ojima, I. In The Chemistry Organic Silicone Com-
7
(a) Li, Z.; Dong, Y.; Lam, J. W. Y.; Sun, J.; Qin, A.; H a€ ußler,
pounds; Patai, S., Rapoport, Z., Eds.; John Wiley: Chichester,
UK, 1989; p 1479; (b) Marciniec, B. Comprehensive Handbook
on Hydrosilylation; Pergamon Press: New York, 1992; pp 130–
M.; Dong, Y.; Sung, H. H. Y.; Williams, I. D.; Kwok, H. S.; Tang,
B. Z. Adv. Funct. Mater. 2009, 19, 905–917; (b) Hatano, K.;
Saeki, H.; Yokota, H.; Aizawa, H.; Koyama, T.; Matsuoka, K.;
Terunuma, D. Tetrahedron Lett. 2009, 50, 5816–5819; (c) Toal,
S. J.; Jones, K. A.; Magde, D.; Trogler, W. C. J. Am. Chem.
Soc. 2005, 127, 11661–11665; (d) Dong, Y.; Lam, J. W. Y.; Qin,
A.; Li, Z.; Liu, J.; Sun, J. Z.; Dong, Y.; Tang, B. Z. Chem. Phys.
Lett. 2007, 446, 124–127; (e) Wang, M.; Zhang, D.; Zhang, G.;
Tang, Y.; Wang, S.; Zhu, D. Anal. Chem. 2008, 80, 6443–6448;
1
37; (c) Mori, A.; Takahisa, E.; Yaamamura, Y.; Kato, T.;
Mudalige, A. P.; Kajiro, H.; Hirabayashi, K.; Nishihara, Y.;
Hiyama, T. Organometallics 2004, 23, 1755–1765; (d) Perry, R.
J.; Karageorgis, M.; Hensler, J. Macromolecules 2007, 40,
3
929–3938.
1
3 (a) Ohshita, J.; Kunai, A. Acta Polym. 1998, 49, 379–403; (b)
Kunai, A.; Toyoda, E.; Nagamoto, I.; Horio, T.; Ishikawa, M.
Organometallics 1996, 15, 75–83; (c) Ohshita, J.; Kanaya, D.;
Watanabe, T.; Ishikawa, M. J. Organomet. Chem. 1995, 489,
(
f) Liu, Z.; Xue, W.; Cai, Z.; Zhang, G.; Zhang, D. J. Mater.
Chem. 2011, 21, 14487–14491; (g) Liu, Y.; Tang, Y.; Barashkov,
N. N.; Irgibaeva, I. S.; Lam, J. W. Y.; Hu, R.; Birimzhanova, D.;
Yu, Y.; Tang, B. Z. J. Am. Chem. Soc. 2010, 132, 13951–13953;
1
65–173; (d) Ohshita, J.; Matsuguchi, A.; Furumori, K.; Hong,
R.-F.; Ishikawa, M. Macromolecules 1992, 25, 2134–2140; (e)
Corriu, R. J. P.; Gerbler, P.; Gu eꢀ rin, C.; Henner, B. J. L.; Jean,
A.; Mutin, P. H. Organometallics 1992, 11, 2507–2513; (f) Wu, H.
J.; Interrante, L. V. Macromolecules 1992, 25, 1840–1841.
(
h) Zhao, Z.; Liu, J.; Lam, J. W. Y.; Chan, C. Y. K.; Qiu, H.;
Tang, B. Z. Dyes Pigments 2011, 91, 258–263.
8
1
(a) Steinfeld, J. I.; Wormhoudt, J. Annu. Rev. Phys. Chem.
998, 49, 203–232; (b) Albert, K. J.; Lewis, N. S.; Schauer, C. L.;
1
4 (a) Sohn, H.; Sailor, M. J.; Magde, D.; Trogler, W. C. J. Am.
Sotzing, G. A.; Stitzel, S. E.; Vaid, T. P.; Walt, D. R. Chem. Rev.
Chem. Soc. 2003, 125, 3821–3830; (b) Sanchez, J. C.; Trogler,
W. C. Macromol. Chem. Phys. 2008, 209, 1527–1540; (c) San-
chez, J. C.; Trogler, W. C. J. Mater. Chem. 2008, 18, 3143–3156;
2000, 100, 2595–2626; (c) Singh, S. J. Hazard. Mater. 2007, 144,
15–28; (d) Lee, Y. H.; Liu, H.; Lee, J. Y.; Kim, S. H.; Kim, S. K.;
Sessler, J. L.; Kim, Y.; Kim, J. S. Chem. Eur. J. 2010, 16,
895–5901; (e) Xu, B.; Wu, X.; Li, H.; Tong, H.; Wang, L. Macro-
(
d) Sohn, H.; Calhoun, R. M.; Sailor, M. J.; Trogler, W. C.
5
Angew. Chem. Int. Ed. 2001, 40, 2104–2105; (e) Sanchez, J. C.;
DiPasquale, A. G.; Rheingold, A. L.; Trogler, W. C. Chem.
Mater. 2007, 19, 6459–6470.
molecules 2011, 44, 5089–5092; (f) Cavaye, H.; Shaw, P. E.;
Wang, X.; Burn, P. L.; Lo, S.-C.; Meredith, P. Macromolecules
2
010, 43, 10253–10261; (g) He, G.; Yan, N.; Yang, J.; Wang, H.;
Ding, L.; Yin, S.; Fang, Y. Macromolecules, 2011, 44,
759–4766; (h) Olley, D. A.; Wren, E. J.; Vamvounis, G.; Fernee,
15 Osborn, J. A.; Jardine, F. H.; Young, J. F.; Wilkinson, G. J.
Chem. Soc. A 1966, 1711–1732.
4
M. J.; Wang, X.; Burn, P. L.; Meredith, P.; Shaw, P. E. Chem.
Mater. 2011, 23, 789–794; (i) Tang, G.; Chen, S. S. Y.; Shaw, P.
E.; Hegedus, K.; Wang, X.; Burn, P. L.; Meredith, P. Polym.
Chem. 2011, 2, 2360–2368.
1
6 Lee, I.-S.; Kwak, Y.-W.; Kim, D.-H.; Cho, Y.; Ohshita, J. J.
Organomet. Chem. 2008, 693, 3233–3239.
7 Lu, P.; Lam, J. W. Y.; Liu, J.; Jim, C. K. W.; Yuan, W.; Chan,
1
C. Y. K.; Xie, N.; Hu, Q.; Cheuk, K. K. L.; Tang, B. Z. Macromole-
cules 2011, 44, 5977–5986.
9
2
(a) Thomas, S. W., III; Joly, G. D.; Swager, T. M. Chem. Rev.
007, 107, 1339–1386; (b) Zahn, S.; Swager, T. M. Angew. Chem.
1
8 Berlman, I. B. Handbook of Fluorescence Spectra of Aro-
Int. Ed. 2002, 41, 4225–4230; (c) Bunz, U. H. F. Chem. Rev. 2000,
matic Molecules; Academic Press: New York and London,
1
00, 1605–1644.
(a) Qin, A.; Lam, J. W. Y.; Tang, B. Z. Macromolecules
010, 43, 8693–8702; (b) Qin, A.; Lam, J. W. Y.; Tang, B. Z.
1
1
971.
(a) Zhao, Z.; Lu, P.; Lam, J. W. Y.; Wang, Z.; Chan, C. Y. K.;
10
9
2
Sung, H. H. Y.; Williams, I. D.; Ma, Y.; Tang, B. Z. Chem. Sci.
011, 2, 672–675; (b) Zhao, Z.; Chen, S.; Deng, C.; Lam, J. W.
Chem. Soc. Rev. 2010, 39, 2522–2544; (c) Liu, J.; Lam, J. W. Y.;
Tang, B. Z. Chem. Rev. 2009, 109, 5799–5867; (d) Lam, J. W. Y.;
Tang, B. Z. Acc. Chem. Res. 2005, 38, 745–754; (e) H a€ ußler, M.;
Tang, B. Z. Adv. Polym. Sci. 2007, 209, 1–58; (f) Lam, J. W. Y.;
Tang, B. Z. J. Polym. Sci. Part A: Polym. Chem. 2003, 41,
2
Y.; Chan, C. Y. K.; Lu, P.; Wang, Z.; Hu, B.; Chen, X.; Lu, P.;
Kwok, H. S.; Ma, Y.; Qiu, H.; Tang, B. Z. J. Mater. Chem. 2011,
2
1, 10949–10956.
2
607–2629; (g) Liu, J.; Zhong, Y.; Lam, J. W. Y.; Lu, P.; Hong,
20 (a) Akhavan, J. The Chemistry of Explosives; Royal Society
of Chemistry: Cambridge, 2004; (b) Peng, Y.; Zhang, A.-J.;
Dong, M.; Wang, Y.-W. Chem. Commun. 2011, 47, 4505–4507.
Y.; Yu, Y.; Yue, Y.; Faisal, M.; Sung, H. H.-Y.; Williams, I.;
Wong, K. S.; Tang, B. Z. Macromolecules 2010, 43, 4921–4936;
2
274
JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY 2012, 50, 2265–2274