Carbazole functionalized silole: Synthesis, aggregation-induced emission, and electrochemical polymerization

Article abstract of DOI:10.1002/bkcs.10332

A carbazole-functionalized silole, 9,9′-(4,4′-(2,3,4,5-tetraphenyl-1H-silole-1,1-diyl)bis(4,1-phenylene))bis (9H-carbazole) (BPCTPS), was prepared through the reaction of dilithium diene with tetrachlorosilane followed by a direct substitution reaction wi

Full text of DOI:10.1002/bkcs.10332

Article
DOI: 10.1002/bkcs.10332
BULLETIN OF THE
A.-R. Lee and W.-S. Han
KOREAN CHEMICAL SOCIETY
Carbazole Functionalized Silole: Synthesis, Aggregation-induced
Emission, and Electrochemical Polymerization
*
Ah-Rang Lee and Won-Sik Han
Department of Chemistry, Seoul Women's University, Seoul 139-774, Korea. *E-mail: wshan@swu.ac.kr
Received September 11, 2014, Accepted March 4, 2015, Published online June 25, 2015
0
0
A carbazole-functionalized silole, 9,9 -(4,4 -(2,3,4,5-tetraphenyl-1H-silole-1,1-diyl)bis(4,1-phenylene))bis
9H-carbazole) (BPCTPS), was prepared through the reaction of dilithium diene with tetrachlorosilane fol-
(
lowed by a direct substitution reaction with (4-(9H-carbazol-9-yl)phenyl)lithium. Combining the carbazole
donor with the silole acceptor resulted in a new type of donor–acceptor (D–A) dyad. Density function theory
(DFT) calculations showed that the highest occupied molecular orbital was localized on the carbazole group
whereas the lowest unoccupied molecular orbital was localized on the silole group. BPCTPS exhibited very
weak emission properties in dilute solution but emitted intensely in the aggregated state, revealing that it was an
aggregation-induced emission (AIE)-active species. Furthermore, addition of electron donating groups to the
silole ring resulted in a slight red shift of both the absorption and emission spectra compared with those of the
reference compound hexaphenylsilole (HTS). The electrochemical properties of BPCTPS were also studied
by cyclic voltammetry (CV), which indicated that the compound formed a cross-linked film on the Pt electrode
via electropolymerization.
Keywords: Silole, Bipolar compound, Aggregation-induced emission, Electropolymerization
1
0
11
Introduction
such as OLEDs, chemo and biosensors, and organic
PVs (OPVs).
12
1,2
Organic molecules are usually used as films or aggregates in
applications such as organic light-emitting diodes (OLEDs),
field-effect transistors (FETs), and photovoltaics (PVs). How-
ever, most of them are highly emissive in dilute solutions but
become weakly luminescent in the aggregate form. This phe3-
nomenon is known as aggregation-caused quenching (ACQ)
and is generally considered as an obstacle in the above-
mentioned applications. To circumvent this problem,
probably the most intriguing approach is based on the aggre-
Carbazole is a well-known electron donor and has been
widely used in phosphorescent blue host materials because
of its wide bandgap, high triplet energy level, and high hole
mobility. Another interesting property of carbazole is that
it can be electropolymerized through the extremely reactive
sites at its 3 and 6 positions. Thus, the electrochemical prep-
aration of conducting polymers has been investigated as an
alternative method to spin-coating. For example, the Advincu-
lar and Ma groups have independently reported electro-
chemically prepared carbazole-based thin films and their
applications in OLEDs and OPVs.
Previously, a nonconjugated ethylene bridge was used to
introduce carbazole units into the silole acceptor for utilization
13
14
15
16
4
gation-induced emission (AIE) phenomenon. AIE is the
opposite of ACQ, and refers to the situation when some non-
fluorescent dyes in solution become efficient emitters in their
aggregate form. Silole is a typical example of an AIE mate-
5
17
rial. It is nonfluorescent when remains isolated in dilute solu-
as a PV active material. It was shown that these donor–
tions but becomes strongly fluorescent in the aggregate state.
In addition, the crystalline phase of siloles exhibits a much6
stronger blue-shifted emission than its amorphous phase.
Thisuniquephenomenonisduetothepresenceofastablelow-
est unoccupied molecular orbital (LUMO), which is the result
acceptor (D–A) type dyads are photovoltaically active
with high thermal stability. In this study, we used a direct
0
0
approach to prepare the linked dyad, 9,9 -(4,4 -(2,3,4,5-tetra-
phenyl-1H-silole-1,1-diyl)bis(4,1-phenylene))bis(9H-carba-
zole) (BPCTPS), which comprises two carbazole units as
electron-donating groups and a silole moiety as the electron-
accepting group. The photophysical properties of the new
compound were investigated by UV–vis absorption and emis-
sion spectroscopy. A theoretical study was also performed to
explore its optical and electronic properties. Finally, its elec-
trochemical properties were studied by cyclic voltammetry
(CV). A highly cross-linked thin film was successfully
obtained by CV through the electropolymerization of the
two carbazole units.
∗
∗
∗
of the σ –π interaction between the σ orbital of the exocyclic
∗
Si C σ-bonds and the π orbitals of the butadiene moiety of
7
the ring. These low-lying LUMO levels of the silole molecule
are responsible for its high electron affinity and electron
8
mobility. Furthermore, in the case of silole polymers, it
was reported that they can be used to detect chemical vapors,
such as the nitro explosive 2,4,6-trinitrotoluene (TNT) and
9
2
,4,6-trinitrophenol (picric acid). Thus, siloles and silole
polymers have been widely utilized in several applications,
Bull. Korean Chem. Soc. 2015, Vol. 36, 1758–1763
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Carbazole Functionalized Silole
Experimental
KOREAN CHEMICAL SOCIETY
4H), 6.97–7.15 (m, 12H), 6.84–6.91 (m, 8H). HR-MS
+
(
FAB). Calcd. for C H N Si (M ) m/z 868.3274, observed
6
4 44 2
General Procedures. All preparative tasks were performed
under an atmosphere of dry nitrogen using standard Schlenk
techniques. Glassware, syringes, magnetic stirring bars, and
needles were dried in a convection oven overnight before
use. THF (tetrahydrofuran) and diethyl ether were freshly dis-
868.3286. Calcd. for C H N Si: C, 88.44; H, 5.10; N, 3.22;
64 44 2
Si, 3.23. Found: C, 88.46; H, 5.11; N, 3.21.
Cyclic Voltammetry. The electrochemical polymerization
and characterization of BPCTPS were carried out using a
BAS 100B electrochemical analyzer (West Lafayette, IN,
USA) at room temperature under argon atmosphere after pur-
ging for at least 5 min. CV scans were recorded in a solution of
dichloromethanecontaining 0.1Mtetrabutylammonium tetra-
1
13
tilled over sodium and potassium benzophenone. H and
spectra were recorded on a Varian Mercury 300 spectrometer
Palo Alto, CA, USA) operating at 300.1 and 75.4 MHz,
C
(
respectively. All proton and carbon chemical shifts were
measured relative to internal residual benzene from the
fluoroborate (TBABF ) as supporting electrolyte. A three-
4
electrode cell system was used, which comprised a platinum
disk (diameter 1.6 mm) electrode as the working electrode,
a platinum wire as the counter electrode, and Ag/AgNO3
(0.1 M) as the reference electrode. The number of electrons
transferred per molecule was determined by performing a lin-
ear sweep voltammetry experiment using a carbon micro-disk
electrode. All potential values were calibrated against the fer-
lock solvent (99.5% CDCl ). Elemental analyses were
3
performed with a Carlo Erba Instruments CHNS-O EA
1108 analyzer (Hindley Green, UK). The absorption and
photoluminescence (PL) spectra were recorded on a Perkin–
Elmer Lambda 2S UV−vis spectrophotometer (Waltham,
MA, USA) and a Perkin–Elmer LS fluorescence spectrometer
+
(Waltham, MA, USA), respectively. Diphenylacetylene,
rocene/ferrocenium (Fc/Fc ) redox couple. The potential
lithium, 1,4-dibromobenzene, carbazole, tetrachlorosilane,
and n-BuLi in 2.5 M hexane were purchased from Aldrich
values measured in this study were then corrected relative to
the saturated calomel electrode (SCE) on the basis of the Fc/
Fc redox potential as 0.58 V vs. that of the SCE, unless oth-
+
(St. Louis, MO, USA) and used without further purification.
9
-(4-Bromophenyl)-9H-carbazole was prepared according
erwise specified.
Electrodeposition. Cross-linked polymer films were pre-
pared on a Pt disk by oxidative successive scans between 0
1
3c
to the literature procedure.
0
Synthesis of 1,1 -Dichloro-2,3,4,5-tetraphenylsilole (2). A
two-neck round-bottomed flask was charged with diphenyla-
cetylene (4.27 g, 24 mmol) and dry THF (20 mL). Clean lith-
ium shavings (347 mg, 50 mmol) were added at room
temperature and the reaction mixture was stirred for 2 h under
and 1.4 V vs. Ag/AgNO at 100 mV/s. After electrochemical
3
polymerization of the film on the Pt electrode, the film was
washed several times with pure dichoromethane followed
by drying under vacuum for 24 h. CV scans of the film were
recorded at scan rates of 100, 50, and 25 mV/s.
N atmosphere. The reaction mixture was diluted with an addi-
2
tional 100 mL of THF, followed by an addition of silicon tet-
rachloride (1.4 mL, 12 mmol) at −78 C. The reaction mixture
was warmed to room temperature and stirred for another 6 h.
After the reaction was complete, the solvent and unreacted sil-
icon tetrachloride were evaporated under vacuum and diethy-
lether was then added to precipitate the LiCl salts, which were
Theoretical Calculations. Density function theory (DFT)
calculations were performed on the platform of the Gaussian
ꢀ
18
09 package. The ground-state geometry was fully optimized
at the DFT level using the B3LYP functional and 6-31G(d,p)
basis set for all atoms. Isodensity plots (contour = 0.03 a.u.)
of the frontier orbitals were visualized by using the
Chem3D Ultra program (Cambridge Soft Corporation,
Cambridge, MA, USA). The excitation energies and
the oscillator strengths for the lowest 30 singlet–singlet transi-
tions at the optimized geometry of the ground state were
obtained through time-dependent DFT (TD-DFT) calcula-
tions using the same basis set and functional as used for the
ground state.
removed by filtration under N atmosphere. The filtrate was
2
ꢀ
concentrated and recrystallized at −20 C to produce 2 as a
greenish yellow solid. Yield: 2.07 g, 38%.
Synthesis of BPCTPS. To a solution of 9-(4-bromophenyl)-
9H-carbazole (1.61 g, 5 mmol) in dry THF (25 mL), n-BuLi in
2
−
.5 M hexane (2.2 mL, 5.5 mmol) was added dropwise at
78 C. After the resulting mixture was stirred at this temper-
ꢀ
ature for 30 min, diluted 2 (0.91 g, 2 mmol) in THF (10 mL)
ꢀ
was added dropwise via a cannula at −78 C. The mixture
Results and Discussions
was then warmed to room temperature and stirred for an addi-
tional 12 h, following which the reaction mixture was poured
into distilled water. The crude products were extracted with
dichloromethane and washed sequentially with water and
brine. The combined organic layers were dried over MgSO4
and the filtrates were evaporated under reduced pressure.
The crude products obtained in this way were purified by flash
chromatography over silica gel using ethylacetate/n-hexane
The synthetic route to BPCTPS is shown in Scheme 1, and the
detailed procedure is described in the Experimental section.
The 1,2,3,4-tetraphenylbutadiene-1,4-dianion was generated
from diphenylacetylene and Li metal in THF solution and
allowed to react with tetrachlorosilane to give 1,1-dichloro-
2,3,4,5-tetraphenylsilole (2). The in situ reaction of 2 with lith-
ium-4-(N-carbazolyl)phenyl (1) resulted in the production of
the target compound BPCTPS in 38% yield after purification
by silica gel chromatography using ethylacetate/hexane 1:10
(v/v). The final product displayed the expected signals on
1
:10 (v/v) as an eluent to afford BPCTPS as a green solid.
1
Yield: 0.87 g, 30%; H NMR (CDCl ): δ 8.16 (d, 4H), 7.99
3
(d, 4H), 7.68 (d, 4H), 7.55 (d, 4H), 7.43 (t, 4H), 7.31 (t,
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Carbazole Functionalized Silole
KOREAN CHEMICAL SOCIETY
Li
THF
Li Li
SiCl4
THF
Si
n-BuLi
2
Br
N
2
Li
N
+
N
N
THF
THF
Si
Cl
Cl
1
2
BPCTPS
Scheme 1. Synthesis of BPCTPS.
Figure 2. A plot of relative emission intensity versus fractions of
water in acetone/water mixed solution.
∗
20
3
68 nmwasattributed tothe π–π transition ofthe silole unit.
Figure 1(b) shows the PL spectrum of BPCTPS in acetone
solution. The compound exhibits weak fluorescence centered
at 486 nm. However, upon addition of water to the solution,
the fluorescence of BPCTPS became increasingly stronger
due to growing AIE. This phenomenon was the consequence
of increasing levels of aggregation, caused by larger water
fractions, in which the silole moieties are insoluble. We
also observed a significant bathochromic shift (13 nm) in
the solvent mixture with the largest water fraction, which indi-
cated that the excited state of BPCTPS involved a charge-
transfer (CT) state. Since the maximum emission of 9-
methylcarbazoleappearedat364 nmandtailed to420 nmwith
significant intensity, the dissipation of carbazole emissions
indicated that an intramolecular energy transfer occurred from
the carbazole groups to the silole moiety in the excited state of
BPCTPS.
Figure 2 shows the magnitude of AIE as a function of the
volume fraction of water. The onset of AIE was observed at
16%, and the maximum enhancement was achieved at 66%
in the acetone/water mixed solvent system. Interestingly, even
though the presence of increasing amounts of water would be
expected to promote aggregation, a dramatic decrease in the
Figure 1. (a) Absorption spectrum of BPCTPS in THF solution. (b)
PL spectra of BPCTPS in acetone/water mixed solution with differ-
ent water fractions (f ).
w
19
1
the H NMR and high-resolution mass spectra (see Supporting
1
Information for H NMR).
Figure 1(a) shows the UV−vis absorption spectrum of
BPCTPS in THF solution. BPCTPS exhibited three absorp-
1
1
tion bands: those at 298 nm ( L
A transition) and 341 nm
a
1
1
(
Lb
A transition) were characteristic of the carbazole
moiety, whereas the lower energy band centered at
19
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Carbazole Functionalized Silole
KOREAN CHEMICAL SOCIETY
AIE effect was observed for larger water fractions, possibly
due to the resulting lower solubility of BPCTPS. Apart from
this, the excited singlet state might be partially quenched by
energy dissociation, because the CT process is favored by
−5.36 and −1.77 eV, respectively, giving rise to a HOMO–
LUMO bandgap (E ) of 3.59 eV. As shown in Figure 3(b),
g
the TD-DFT transition energies for the first excited states cor-
respondedqualitativelytotheexperimental values. Thelowest
energy absorption can be described as predominantly HOMO
1
7
the aggregated phase.
∗
The observed photophysical properties were further inves-
tigated by conducting quantum chemical calculations for
BPCTPS using the B3LYP/6-31G(d,p) level of theory.
Figure 3 shows selected molecular orbitals and the calculated
absorption spectrum for BPCTPS. In Figure 3(a), it can be
seen that the highest occupied molecular orbital (HOMO) is
mainly located on the electron-donating phenyl carbazole
!LUMO in nature (39%), with an n–π transition from the
electron-donatingPCunitstotheelectron-acceptingsiloleunit
∗
as well as a HOMO–2 !LUMO (32%) π–π transition within
the butadiene fragment of the silole ring.
The electrochemical behavior of BPCTPS was determined
by CV at room temperature in presence of 0.1 M TBABF as
4
supporting electrolyte in anhydrous dichloromethane under
(
PC) unit. It is well known that a low-lying LUMO in silole
N at various scan rates (details of the electrodes are provided
in the Experimental section). It was found that BPCTPS
2
∗
results from unique orbital interactions between the σ orbital
∗
of the exocyclic Si C σ-bonds and the π orbital of the buta-
exhibited irreversible oxidation and reduction waves, as
7
22
diene moiety. As shown in Figure 3(a), the LUMO is mainly
observedforothersilole derivatives. Fromthefirstoxidation
localized on the C Si C and C C bonds of the silole moiety
in BPCTPS.
onset potential, the HOMO energy level of BPCTPS was esti-
mated to be ~ –5.53 eV (calibrated using a ferrocene, 4.8 eV
below the vacuum level) and the LUMO energy level was cal-
culated to be −2.04 eV from the absorption edge of the
optical absorption spectra of BPCTPS. Hence, there was a
good correspondence between the experimental and calcu-
lated values.
TD-DFT methods are useful for assigning and understand-
2
1
ing the absorption spectra. Therefore, a TD-DFT calculation
was conducted, and the selected oscillation strength (f) and
electronic transitions are displayed in Figure 3(b). The calcu-
lated HOMO and LUMO energy levels of BPCTPS were
Carbazole can be electropolymerized on transparent con-
ducting oxides (TCOs), such as indium tin oxide (ITO),
14
through its extremely reactive sites at the 3 and 6 positions.
Therefore, we carried out the electropolymerization of
BPCTPS ona Pt diskbyusing CV. The electropolymerization
of BPCTPS became apparent after five repeated scans, after
which an increase in both the anodic and cathodic peak cur-
rents was observed during continuous CV scans (see
Figure 4). The formation of the deposited film was confirmed
by immersing the electropolymerized electrode into a 0.1
M dichloromethane solution of TBABF electrolyte and mea-
4
suring the current at scan rates of 100, 50 and 25 mV/s
(Figure 4(b)). The peak currents were proportional to the scan
rates, and the difference between the anodic and the cathodic
peak potentials were not changed, which is a typical property
23
of a film deposited on an electrode.
Conclusions
We have prepared a silole dyad, BPCTPS, consisting of two
PC units as electron donors and a silole unit as an electron
acceptor. BPCTPS exhibited AIE when water was added to
a solution of the compound. A dramatic decrease in the
AIE, together with a significant bathochromic shift, was
observed for larger water fractions (>70%), indicating that
the excited state of BPCTPS involved a CT state. Further-
more, an electrodeposited film was successfully formed by
electropolymerization using CV. The electrochemical prepa-
ration of TCO substrates is widely applied in organic electron-
ics, such as in OLEDs andOPVs; therefore, an investigation of
the application of BPCTPS in organic electronics has been
currently undertaken in our laboratory.
Figure 3. (a) Selected molecular orbitals and (b) computed absorp-
tion spectrum for BPCTPS.
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Carbazole Functionalized Silole
KOREAN CHEMICAL SOCIETY
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Acknowledgment. This work was supported by a research
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Supporting Information. H NMR spectrum of BPCTPS is
available in the online version of this article.
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Bull. Korean Chem. Soc. 2015, Vol. 36, 1758–1763
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Carbazole Functionalized Silole
KOREAN CHEMICAL SOCIETY
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Bull. Korean Chem. Soc. 2015, Vol. 36, 1758–1763
© 2015 Korean Chemical Society, Seoul & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.bkcs.wiley-vch.de 1763