New AIEgens containing tetraphenylethene and silole moieties: Tunable intramolecular conjugation, aggregation-induced emission characteristics and good device performance

Article abstract of DOI:10.1039/c4tc02631d

Three aggregation-induced emission luminogens (Si-pTPE, Si-tPE and Si-mTPE) were successfully obtained by the covalent incorporation of tetraphenylethene into a dibenzosilole core. Through sharing a benzene ring and changing the linkage mode between TPE a

Full text of DOI:10.1039/c4tc02631d

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New AIEgens containing tetraphenylethene and silole
moieties: tunable intramolecular conjugation,
aggregation-induced emission characteristics, and good
device performance†
Jie Yang,a Ning Sun,b Jing Huang,a Qianqian Li,a Qian Peng,c Xi Tang,d Yongqiang
Dong,d Dongge Ma*b and Zhen Li*a
Three aggregation-induced emission (AIE) luminogens (Si-pTPE, Si-tPE and Si-mTPE) were
successfully obtained by the covalent incorporation of tetraphenylethene to dibenzosilole core. Through
sharing benzene ring and changing link mode between TPE and silole core, their emission colours were
tuned from green to sky blue even deep blue. The non-doped OLED device based on Si-tPE exhibits sky
blue light with high luminance (up to 27161 cd m-2) and high current, power and external quantum
efficiencies (up to 8.04 cd A-1, 6.17 lm W-1 and 3.38%, respectively).
Introduction
BTPEMTPS (Figure 1), also possessed relatively good performance
(6.4 cd A-1), with the electroluminescence emission peak of 552 nm,
Recently, AIEgens, one special kind of luminogens exhibiting weak
luminescence in solutions but much, even dramatically enhanced
emission in aggregation state, such as solid state or nanoparticles,
have attracted increasing attention, due to their totally different
emissive behaviour against the notorious aggregation-caused
quenching (ACQ) effect and huge potential applications as light
emitting diodes (LED), chemo- and bio-sensors, fluorescent patterns,
et al., since their first report in 2001 by the group of Ben Zhong
Tang.1 As a typical example, 1-methyl-1,2,3,4,5-pentaphenylsilole
(MPPS, one famous molecule of the silole family, Figure 1), with a
highly twisted structure, demonstrated a very high efficiency of 8%
when acting as the emissive layer in the corresponding LED device,
which approached the theoretical limitation of the OLEDs based on
fluorescent luminogens.2 Stimulated by this exciting result, many
efficient AIEgens have been designed and showed satisfactory
performance in their related LED devices, for example, once bulky
dimesitylboryl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, and
9,9-spirobifluorenyl substituents were introduced into the 2,5-
positions of silole rings, the resulted AIEgens all exhibited
outstanding EL performance, even up to 16.0 cd A-1.3 However, it
was a little pity that similar to other fluorescent luminogens, there
were few reports concerning the blue AIE fluorophors, once again
showing the difficulty to achieve good blue organic light-emitting
materials, derived from their intrinsic wide band gap.4 Interestingly,
once incorporating TPE moieties, another famous AIE construction
block with inherent blue emission to MPPS core, the resultant 2,5-
longer than that of MPPS, as the result of the prolonged conjugation
length.5
Recently, by simply sharing benzene ring, utilizing different
linkage modes, and increasing the twisting degree of the molecules
in the presence of additional groups, we have successfully
constructed some blue AIEgens, which exhibited good performance
as emitting layer in OLEDs, partially due to their AIE
characteristics.6 Thus, is it possible to apply these strategies to the
above mentioned TPE-silole system, to develop some new AIEgens
with blue emissions, but not the green one as 2,5-BTPEMTPS?
Figure 1. Chemical structures of TPE, MPPS, dibenzosilole and 2,5-
BTPEMTPS.
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Scheme 1. Synthetic route to Si-pTPE, Si-tPE and Si-mTPE.
To control the conjugation length and simplify the synthesis, in compound
4 and dichlorodiphenylsilane. The corresponding
addition to the above mentioned strategies, we utilized another diboronic ester for compound 5 was successfully obtained in a good
silole-derivative, dibenzosilole, instead of MPPS, as the construction yield using Pd(dppf)2Cl2 as the catalyst. Compound 7, 8 and 9 were
block, and incorporated TPE moieties to yield three AIEgens (Si- synthesized according to the literatures.6,8 Finally, the desired
pTPE, Si-tPE and Si-mTPE), in which the approaches of para- products of Si-pTPE, Si-tPE and Si-mTPE were successfully
position linkage, sharing benzene ring and meta-position linkage afforded through the Suzuki cross-coupling reactions and they were
between silole and TPE groups, were applied respectively. The all purified by column chromatography on silica gel using petroleum
results partially confirmed our idea. The OLED devices based on ether and chloroform as eluent, and fully characterized by 1H and 13
C
NMR, mass spectrometry, and elemental analysis (Figure S1- S10).
these AIEgens exhibit green, sky blue and deep blue emission,
respectively. Among them, Si-tPE shows the best performance of
8.04 cd A-1 with sky blue emission. Herein, we would like to present
the syntheses, characterization, photophysical properties, theoretical
calculation and LED device performance of these AIEgens in detail.
100
80
60
40
20
0
Si-pTPE
Si-tPE
Si-mTPE
Results and discussion
Synthesis
Scheme 1 shows the synthetic route to Si-pTPE, Si-tPE and Si-
mTPE, and the detailed procedures are presented in the experimental
section.7 First, we prepared compound 2 through Ullmann reaction
under the catalyst of copper powder in a high yield, then nitro-
groups were reduced to yield compound 3. The amidogen of
compound 3 was replaced by iodine, and the key intermediate,
compound 5, was synthesized through ring-closing reaction between
50
150
250
350
450
550
Temperature (oC)
Figure 2. TGA thermograms of Si-pTPE, Si-tPE and Si-mTPE recorded
under N2 at a heating rate of 10 oC/min.
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Table 1. The thermal, electrochemical and photophysical data of Si-pTPE, Si-tPE and Si-mTPE.
d
e
c
Tda
(oC)
458
421
411
Tg
Egb
Eox
(V)
EHOMO
(eV)
5.47
5.40
5.60
ε f
(× 104 M-1 cm-1)
5.87
PL λmax (aggr) g
ELUMO
(eV)
2.45
λabs
PL λmax (film)
(oC)
196
107
---
(eV)
3.02
2.99
3.32
(nm)
498
498
474
(nm)
(nm)
Si-pTPE
Si-tPE
1.15
1.08
1.27
359
362
325
498
496
468
2.41
2.28
3.31
Si-mTPE
7.45
a 5% weight loss temperature measured by TGA under N2. b Band gap estimated from optical absorption band edge of the solution. c Calculated from the onset
oxidation potentials of the compounds. d Estimated using empirical equations ELUMO = EHOMO + Eg. e Observed from absorption spectra in dilute THF solution.
f Molar extinction coefficient. g Determined in THF:H2O = 1:99 solution.
Thermal properties
carefully, although the ignorable difference was the linkage mode
between the TPE moieties and dibenzosilole, there was a big
difference, as large as 34 nm, in their maximum absorption
wavelength. This confirmed again the powerful control of
intramolecular conjugation by simply changing the linkage mode,
We carried out TGA (thermo gravimetric analysis) and DSC
(differential scanning calorimetry) to examine their thermal
properties. As shown in Figure 2, they were all thermally stable, with
their thermal-decomposition temperatures (Td, corresponding to 5%
weight loss) higher than 410 oC. Also, Si-pTPE and Si-tPE exhibited
relatively high glass transition temperatures (Tg), namely 196 and
realizing our design idea.
8000
f
(vol %)
w
7000
6000
5000
4000
3000
2000
1000
0
o
0
107 C, respectively (Table 1, Figure S11). Unfortunately, the DSC
10
20
30
40
50
60
70
80
90
95
99
curve of Si-mTPE showed no obviously Tg. Thus, the good thermal
stability with high Td and Tg values would contribute to the long
lifetime, when they were made into OLED devices.9
1.0
0.8
Si-pTPE
Si-mTPE
Si-tPE
0.6
390
440
490
540
590
640
690
Wavelength (nm)
Figure 4. (A) PL spectra of Si-pTPE in THF–H2O mixtures with different
water fractions. Concentration (M): 14.1; excitation wavelength (nm): 370.
0.4
0.2
0.0
32
24
300
350
400
450
500
Si-pTPE
Si-mTPE
Si-tPE
Wavelength (nm)
Figure 3. UV spectra in THF solution. Concentration (): 14.1, 11.6 and
12.1 for Si-pTPE, Si-tPE and Si-mTPE, respectively.
16
AIE properties and theoretical calculations
8
0
In the UV-vis spectra of Si-pTPE, Si-tPE and Si-mTPE recorded in
THF solution (Figure 3), their maximum absorption peaks located at
359, 362 and 325 nm respectively. The results indicated that Si-
mTPE exhibited the weakest conjugation, while Si-pTPE and Si-tPE
were almost the same. In comparison with that of 2,5-BTPEMTPS
(395 nm), all these three compounds possessed much blue-shifted, as
the result of their controlled intramolecular conjugation effect.
Analyzing the absorption behaviours of Si-pTPE and Si-mTPE
0
20
40
60
80
100
Water fraction (vol%)
Figure 5. Plots of fluorescence quantum yields of Si-pTPE, Si-tPE and Si-
mTPE determined in THF/H2O solutions by using 9,10-diphenylanthracene
(Ф = 90% in cyclohexane) as standard versus water fractions.
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HOMO
LUMO
Optimized
Structures
Si-pTPE
Si-tPE
Si-mTPE
Figure 6. Calculated molecular orbital amplitude plots of LUMO, HOMO levels and optimized molecular structures for Si-pTPE, Si-tPE and Si-mTPE.
In order to investigate the possible AIE characteristics of these mTPE partly overlapped, which might lead to the ICT effect. As to
three molecules, their fluorescent behaviours were studied. We chose Si-mTPE, its molecular structure was much twisted, which would
tetrahydrofuran as the good solvent while water as the poor one. As weaken the ICT effect. So, once a large amount of water was added,
shown in Figure 4 and Figure S12，Si-pTPE, Si-tPE and Si-mTPE the polarity of the mixed solvent increased accordingly, as a result,
were all nonemissive in pure THF, however, after a large amount of the ICT effect occurred in the case of Si-pTPE much easier, directly
water was added, they all emitted strong fluorescence. Figure 5 leading to the red-shifted emission. On the other hand, with addition
demonstrated the changes of their fluorescence quantum yield (ΦF) of water, the transformation from crystalline state to amorphous one
in THF/water mixtures with different water fractions (fw), which would also contribute to it. But as to the cases of Si-tPE and Si-
mTPE, nearly no influences were observed.
enabled fine-tuning of the solvent polarity and the extent of solute
aggregation. In pure THF solution, they were all less than 0.3%,
while at a fw value of 99%, the ΦF of Si-pTPE and Si-tPE exceeded
25%, while that of Si-mTPE was limited to 13%, only about half to
its analogue, possibly due to their different molecular structures.
Anyhow, these three luminogens are all AIE-active.
Although their crystal structures were not obtained, the calculated
ones could still give some explanations. The geometries of the
molecules have been optimized by using DFT calculations with the
Gaussian 09 program. In particular, we used the B3LYP exchange-
correlation functional and a 6-31g* basis set. As shown in Figure 6,
the structure of Si-mTPE was much more twisted than Si-pTPE and
Si-tPE, which might provide more room for the rotation of the
phenyl rings even in aggregation state, thus, much energy would be
consumed through the intramolecular rotation, resulting in its lower
ΦF.6
Electrochemical Properties
The electrochemical properties of Si-pTPE, Si-tPE and Si-mTPE
were investigated by cyclic voltammetry (CV) (Figure S13). The
HOMO energy levels were calculated to be 5.47, 5.40 and 5.60 eV
respectively, according to the following equation: HOMO = - (4.8 -
E(Fc/Fc+) + Eox) eV in which E(Fc/Fc+) is 0.48 eV, suggesting that Si-tPE
might possess the best hole-injection ability among the three
AIEgens. Their LUMOs could be obtained from optical band gap
energies (estimated from the onset wavelength of their UV
absorptions) as 2.45, 2.41 and 2.28 eV for Si-pTPE, Si-tPE and Si-
mTPE respectively. Thus, Si-pTPE and Si-tPE possessed better
electronic injection capacity, possibly affecting their performance in
OLED devices largely.
Also when we investigated their AIE characteristics, we found the
emission of Si-pTPE was red-shifted about 80 nm after the addition
Electroluminescence
of excessive water (fw > 80%), while no obvious change for those of Due to their good thermal stabilities and efficient light emissions in
Si-tPE and Si-mTPE. This could be explained from the distribution the solid state, we fabricated their non-doped OLED devices with a
of their different electron clouds. As shown in Figure 6, the configuration of ITO/MoO3 (10 nm)/NPB (60 nm)/EML (15
molecular orbital amplitude plots of the HOMO and LUMO energy nm)/TPBi (30 nm)/LiF (1 nm)/Al. In these OLED devices, MoO3,
levels for Si-tPE overlapped perfectly, indicating no intramolecular NPB worked as the hole-injection, hole transporting layer
respectively, and TPBi acted as electron transporting as well as hole
charge transfer (ICT) existed. However, those of Si-pTPE and Si-
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Table 2. EL performance of Si-pTPE, Si-tPE and Si-mTPE.
λEL
Von
Lmax
ηP, max
ηC, max
CIE
ηext, max
(%)
(nm)
512
(V)
3.5
(cd m-2)
28718
(lm W-1)
5.57
(cd A-1)
7.40
(x, y)
Si-pTPE
2.92
3.38
1.21
0.21, 0.37
Si-tPE
488
432
3.0
3.7
27161
4411
6.17
1.18
8.04
1.39
0.20, 0.33
0.16, 0.12
Si-mTPE
Abbreviations: Von = turn-on voltage at 1 cd m-2, Lmax = maximum luminance, ηP, max, ηC, max and ηext, max = maximum power, current and
external quantum efficiencies, respectively. CIE = Commission International de l’Eclairage coordinates.
9
8
7
6
5
4
3
2
1
The device based on Si-pTPE also presented a good performance
with a maximum current efficiency (ηC, max) of 7.40 cd A−1, but its
EL spectrum was red-shifted to 512 nm, which was out of the blue
area. So only removing a phenyl ring between the tetraphenylethene
group and dibenzosilole core, the EL emission based on Si-tPE was
blue-shifted about 24 nm, in comparison with Si-pTPE while its
current efficiency was higher. The cheerful performance might be
owed to the reason that Si-tPE was in a more planar conformation
and showed a better carrier mobility, but the length of the
conjugation is shorter for a lack of phenyl ring which will contribute
to its blue-shift. As for Si-mTPE, the device showed an emission
centred at 432 nm (deep blue). Compared to its PL spectra of the thin
film (468 nm) and nanoaggregates (474 nm), its EL spectrum was
blue-shifted more than 35 nm, manifesting the emitting layer mainly
existed in crystal.10 Generally, crystals are a two-edged sword: on
one hand, it would be helpful to construct blue materials, but on the
other, the LED device based on it will exhibit an inferior
performance, since the grain boundaries between adjacent
crystallites act as traps for charge carriers.11 The device based on Si-
mTPE showed an unsatisfactory performance (1.39 cd A-1)
compared to its analogues. Rather than Si-pTPE, although the
ignorable difference was the linkage mode between the TPE
moieties and dibenzosilole for Si-mTPE, there was a big difference,
as large as 80 nm, in their maximum EL emission. This confirmed
the powerful control of intramolecular conjugation by simply
Si-pTPE
Si-mTPE
Si-tPE
0
0.01
0.1
1
10
100
1000
Current Density (mA/cm2)
Figure 7. Changes in current efficiency with the current density, Device
configuration: ITO/MoO3 (10 nm)/NPB (60 nm)/Si-pTPE or Si-mTPE or Si-
tPE (15 nm)/TPBi (30 nm)/LiF (1 nm)/Al.
blocking layer. Si-pTPE, Si-tPE and Si-mTPE served as emitters. Fig
7 and Figure S14 showed the current density-voltage-brightness (J-
V-L) characteristics, current efficiency, power efficiency and
external quantum efficiency versus current density curves of the
OLEDs. As listed in Table 2, all the devices turned on at a low
voltage from 3.0 to 3.7 V, showing small injection barriers from
transporting layers in the devices. Among them, Si-tPE exhibited the
best performance, with a maximum luminance (Lmax) of 27161 cd
m−2, a maximum current efficiency (ηC, max) of 8.04 cd A−1, a changing the linkage mode.
maximum power efficiency (ηP, max) of 6.17 lm W−1 and a maximum
external quantum efficiency (ηext, max) of 3.38%. The EL spectrum of
the device peaked at 488 nm (sky blue), which was slightly blue-
shifted from the PL peaks of the thin film (496 nm) and
nanoaggregates (498 nm) of Si-tPE, indicating that the emitting layer
partly crystallized (Figure 8).
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at a scan rate of 100 mV s-1 with 0.1 M tetrabutylammonium
1.0
0.8
0.6
0.4
0.2
0.0
perchlorate (purchased from Alfa Aesar) as the supporting
electrolyte, in anhydrous dichloromethane solution purged with
nitrogen. The potential values obtained in reference to the Ag/Ag+
electrode were converted to values versus the saturated calomel
electrode (SCE) by means of an internal ferrocenium/ferrocene
(Fc+/Fc) standard.
Si-pTPE (Film)
Si-tPE (Film)
Si-mTPE (Film)
Si-pTPE (EL)
Si-tPE (EL)
Si-mTPE (EL)
Computational details
The geometrical and electronic properties were optimized at
B3LYP/6-31g* level using Gaussian 09 program. The molecular
orbitals were obtained at the same level of theory.
390 440 490 540 590 640 690
Wavelength (nm)
OLED device fabrication and measurement
Figure 8. PL and EL spectra of solid thin films of Si-pTPE, Si-tPE and Si-
mTPE. The thin films were spin-coated onto ITO glass from dilute THF
solution with concentrations of 1 mg mL-1.
The EL devices were fabricated by vacuum deposition of the
materials at a base pressure of 5×10-6 torr onto glass pre-coated with
a layer of indium tin oxide (ITO) with a sheet resistance of 25
Ω/square. Before the deposition of an organic layer, the clear ITO
substrates were treated with oxygen plasma for 3 min. The
deposition rate of organic compounds was 0.9-1.1 Å s-1. After the
hole-injection layer MoO3, hole-transporting layer 1,4-bis(1-
naphthylphenyl-amino)biphenyl (NPB), emission layer, electron-
transporting layer 1,3,5-tris(N-phenyl-benzimidazol-2-yl)benzene
(TPBI), and lithium fluoride (LiF) were deposited by the thermal
evaporation under a base vacuum of ~10-6 torr, aluminium (Al) metal
was evaporated in another vacuum chamber without breaking the
vacuum. The J–V–L of the devices was measured with a Keithley
2400 Source meter and Keithley 2000 Current meter. The EL spectra
were measured by JY SPEX CD3000 fluorescence
spectrophotometer and PR650 Spectra Scan Photometer. All
measurements were carried out at room temperature under ambient
conditions.
Conclusions
In summary, three AIEgens (Si-pTPE, Si-tPE and Si-mTPE) based
on tetraphenylethene and silole were obtained. These three new
compounds were nonemissive in the solution state, but highly
emissive when aggregated, showing typical AIE effect. They
exhibited high thermal stability and great EL performance. The best
performance was achieved for Si-tPE (Lmax of 27161 cd m−2, ηC, max
of 8.04 cd A−1, ηP, max of 6.17 lm W−1 and ηext, max of 3.38% at 488
nm), thanks to the high electron mobility of silole and AIE nature of
TPE. Just through small structural modulation of sharing benzene
ring and changing link mode between TPE and silole core, their EL
spectra were tuned from green to sky blue even deep blue. We may
believe that, inspired by these preliminary results, many other AIE
luminophores with better performance and blue emission could be
further developed.
Preparation of compounds
Experimental section
Solvents for chemical synthesis were purified according to the
standard procedures. Compound 7, 8 and 9 were synthesized
according to the literatures.6,8 All other chemicals and reagents were
obtained from commercial sources and used as received.
Characterization
1H and 13C NMR spectra were measured on a Mecuryvx300
spectrometer or Bruker Advance III (400 MHz) spectrometer.
Elemental analyses of carbon and hydrogen were measured on a
Perkin-Elmer microanalyzer. Mass spectra were measured on a
Bruker BIFLEX Ⅲ TOF or JEOL LMS-HX-110 mass
spectrophotometer. UV-vis absorption spectra were recorded on a
Synthesis of compound 212
Compound 1 (14.1 g, 50 mmol) and copper power (7.0 g, 109 mmol)
in DMF (55 mL) were added into a 200 mL Schlenk tube, The
resultant mixture was stirred for 1 hour under argon at 125 oC. After
cooling to room temperature, the brown residue was filtered off and
washed with 20 mL of toluene. Then the filtrate was distilled under
reduced pressure. The crude product was purified by column
chromatography on silica gel using petroleum ether/chloroform (v/v
= 4/1) as eluent, a yellow solid was finally obtained in the yield of
Shimadzu
UV-2500
recording
spectrophotometer.
Photoluminescence spectra were recorded on a Hitachi F-4500
fluorescence spectrophotometer. Differential scanning calorimetry
(DSC) was performed on a NETZSCH DSC 200 PC unit at a heating
o
o
rate of 15 C min-1 from room temperature to 300 C under argon.
Thermogravimetric analysis (TGA) was undertaken with
NETZSCH STA 449C instrument. The thermal stability of the
samples under a nitrogen atmosphere was determined by measuring
a
1
91% (9.18 g). H NMR (400 MHz, CDCl3) δ (ppm): 8.38-8.39 (d,
o
2H), 7.82-7.85 (m, 2H), 7.15-7.17 (d, 2H).
their weight loss while heating at a rate of 10 C/min from 50 to 550
oC. Cyclic voltammetry (CV) was carried out on a CHI voltammetric
analyzer in a three-electrode cell with a Pt counter electrode, a
Ag/AgCl reference electrode, and a glassy carbon working electrode
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Synthesis of compound 312
Synthesis of Si-pTPE
Tin powder (5.94 g, 50 mmol) was added in batches to a stirred Compound 6 (205 mg, 0.35 mmol), compound 7 (296 mg, 0.72
solution of compound 2 (4.02 g, 10 mmol) in 48 mL ethanol and 30 mmol), Pd(PPh3)4 (0.10 g, 0.08 mmol) and potassium carbonate (483
mL 32% w/w aqueous HCl , then the mixture was heated to reflux mg, 3.5 mmol) in 15 mL of tetrahydrofuran and 5 mL of distilled
for 2 hours. After cooling to room temperature, NaOH solution (2 water were added into a 100 mL Schlenk tube. The resultant mixture
mmol L-1) was added until the solution was alkaline. Then, the was refluxed for 1 hour under nitrogen, then extracted with
resultant solution was extracted with dichloromethane, dried over dichloromethane for several times. The combined organic extracts
anhydrous Na2SO4 and concentrated by rotary evaporation. The were dried over anhydrous Na2SO4 and concentrated by rotary
crude product was purified by column chromatography on silica gel evaporation. The crude product was purified by column
using petroleum ether/tetrahydrofuran (v/v = 20/1) as eluent, a light chromatography on silica gel using petroleum ether/chloroform (v/v
1
brown solid was finally obtained in the yield of 85%. H NMR (400 = 4/1) as eluent, a light green solid was finally obtained in the yield
1
MHz, CDCl3) δ (ppm): 6.94 (s, 6H), 3.75 (s, 4H).
of 43%. H NMR (300 MHz, CDCl3) δ (ppm): 7.90-7.94 (d, 4H),
7.66-7.69 (d, 6H), 7.30-7.40 (m, 10H), 7.06-7.10 (m, 34H). 13C (75
MHz, CDCl3) δ (ppm): 147.8, 144.0, 143.1, 141.3, 140.1, 138.8,
137.0, 135.9, 132.7, 132.5, 132.1, 131.6, 130.5, 129.8, 128.4, 128.1,
127.9, 126.7, 126.3, 121.8. MS (MALDI TOF), (m/z): 994.4197
([M]+, calcd for C76H54Si, 994.3995. Anal. Calcd for C76H54Si: C,
91.71, H, 5.47. Found: C, 90.93, H, 5.59.
Synthesis of compound 412
Compound 3 (7.16 g, 20 mmol) and p-toluenesulfonic (17.18 g, 90.4
mmol) were dissolved in acetonitrile (200 mL) at 0 C. After stirred
for further 20 min, a solution of NaNO2 (4.14 g, 60 mmol) and KI
(12.45 g, 75 mmol) in water (40 mL) was added dropwise into it, the
resultant mixture was warmed to room temperature and stirred
overnight, then extracted several times with dichloromethane, dried
o
Synthesis of Si-tPE
over anhydrous Na2SO4 and concentrated by rotary evaporation. The Compound
6 (220 mg, 0.36 mmol), compound 8 (246 mg, 0.74
crude product was purified by column chromatography on silica gel mmol), Pd(PPh3)4 (0.10 g, 0.08 mmol) and potassium carbonate
using pure petroleum ether as eluent, a white solid was finally (497 mg, 3.6 mmol) in 15 mL of tetrahydrofuran and 5 mL of
obtained in the yield of 25%.
distilled water were added into a 100 mL Schlenk tube. The
resultant mixture was refluxed for 1 hour under nitrogen, then
extracted with dichloromethane for several times. The
combined organic extracts were dried over anhydrous Na2SO4
and concentrated by rotary evaporation. The crude product was
purified by column chromatography on silica gel using
petroleum ether/chloroform (v/v = 4/1) as eluent, a light green
Synthesis of compound 513
Compound 3 (1.8 g, 3.19 mmol) in anhydrous tetrahydrofuran (30
mL) was treated with n-BuLi (5 mL, 2.25 M in hexane, 11.25 mmol)
o
o
at -78 C for 30 min. After stirred at -78 C for another 2 hours,
dichlorodiphenylsilane (1.6 g, 6.38 mmol) was added dropwise into
it, then the mixture was warmed to room temperature and stirred
overnight. The solution was quenched with water and extracted
several times with dichloromethane. The organic layer was dried
over anhydrous Na2SO4 and concentrated by rotary evaporation. The
crude product was purified by column chromatography on silica gel
using petroleum ether/dichloromethane (v/v = 10/1) as eluent, a
white solid was finally obtained in the yield of 35%.1H NMR (400
MHz, CDCl3) δ (ppm): 7.83-7.84 (d, 2H), 7.70-7.72 (d, 2H), 7.58-
7.62 (m, 6H), 7.40-7.46 (m, 2H), 7.36-7.38 (t, 4H).
1
solid was finally obtained in the yield of 76%. H NMR (300
MHz, CDCl3) δ (ppm): 7.57-7.60 (d, 2H), 7.44 (s, 2H), 7.35-
7.37 (d, 2H), 7.22 (s, 2H), 7.03-7.16 (m, 38H). 13C (75 MHz,
CDCl3) δ (ppm): 146.9, 144.1, 144.0, 143.5, 141.2, 141.1,
137.4, 135.6, 135.4, 134.1, 133.2, 131.7, 129.9, 128.2, 128.0,
127.9, 126.7, 120.9. HRMS, (m/z): 842.3362 ([M]+, calcd for
C64H46Si, 842.3369. Anal. Calcd for C64H46Si: C, 91.17, H,
5.50. Found: C, 90.66, H, 5.80.
Synthesis of Si-mTPE
Synthesis of compound 6
Compound 6 (205 mg, 0.35 mmol), compound 9 (296 mg, 0.72
mmol), Pd(PPh3)4 (0.10 g, 0.08 mmol) and potassium carbonate (483
mg, 3.5 mmol) in 15 mL of tetrahydrofuran and 5 mL of distilled
water were added into a 100 mL Schlenk tube. The resultant mixture
was refluxed for 1 hour under nitrogen, then extracted with
dichloromethane for several times. The combined organic extracts
were dried over anhydrous Na2SO4 and concentrated by rotary
evaporation. The crude product was purified by column
chromatography on silica gel using petroleum ether/chloroform (v/v
= 4/1) as eluent, a white solid was finally obtained in the yield of
A mixture of compound 5 (1.02 g, 2.07 mmol), 4,4,4’,4’,5,5,5’,5’-
octamethyl-2,20-bi(1,3,2-dioxaborolane) (1.32 g, 5.19 mmol),
potassium acetate (1.42 g, 14.49 mmol), and Pd(dppf)2Cl2 (150 mg,
0.2 mmol) in anaerobic 1,4-dioxane (45 mL) were refluxed under
nitrogen for 12 h, and then water (20 mL) was added. The crude
product was extracted with dichloromethane. The organic layer was
dried over anhydrous Na2SO4 and concentrated by rotary evaporation.
The crude product was purified by column chromatography on silica
gel using petroleum ether/dichloromethane (v/v = 3/1) as eluent, a
1
55%. H NMR (300 MHz, CDCl3) δ (ppm): 7.80-7.83 (d, 2H), 7.65-
7.67 (d, 4H), 7.33-7.42 (m, 14H), 7.20-7.21 (d, 4H), 6.88-7.10 (m,
30H). 13C (100 MHz, CDCl3) δ (ppm): 146.3, 143.0, 142.7, 142.6,
1
white solid was finally obtained in the yield of 65%. H NMR (300
MHz, CDCl3) δ (ppm): 8.20 (s, 2H), 7.93-7.94 (t, 4H), 7.64-7.67 (m,
4H), 7.34-7.40 (m, 6H), 1.35 (s, 24H).
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 7

View Article Online
Journal of Materials Chemistry C
DOI: 10.1039/C4TC02P63a1gDe 8 of 9
ARTICLE
Journal Name
142.5, 140.2, 139.8, 139.4, 139.0, 135.5, 134.7, 131.7, 131.5, 130.4,
130.3, 130.0, 129.2, 129.1, 128.5, 127.1, 127.0, 126.9, 126.7, 126.6,
125.6, 125.5, 125.4, 124.1, 120.3. HRMS, (m/z): 995.4075 ([M+1]+,
calcd for C76H55Si, 995.4073. Anal. Calcd for C76H54Si: C, 91.71, H,
5.47. Found: C, 91.59, H, 5.56.
6
7
(a) J. Huang, X. Yang, J. Wang, C. Zhong, L. Wang, J. Qin and Z. Li,
J. Mater. Chem., 2012, 22, 2478; (b) J. Huang, N. Sun, Y. Dong, R
Tang, P. Lu, P. Ca, Q. Li, D. Ma, J. Qin and Z. Li, Adv. Funct. Mater.,
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Acknowledgements
We are grateful to the National Fundamental Key Research Program
(2013CB834701), and the National Natural Science Foundation of
China (no. 21161160556) for financial support.
8
9
D. Jana, B. K. Ghorai, Tetrahedron, 2012, 68, 7309.
Notes and references
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a Department of Chemistry, Hubei Key Lab on Organic and Polymeric Opto-
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Institute of Applied Chemistry, The Chinese Academy of Sciences
Changchun 130022, China. E-mail: mdg1014@ciac.jl.cn.
c
Key Laboratory of Organic Solids, Beijing National Laboratory
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Polymer Journal, 2011, 43, 58.
forMolecular Science (BNLMS), Institute of Chemistry, Chinese Academy of
Sciences, 100190 Beijing, China.
d Department of Chemistry, Beijing Normal University, Beijing, 100875, P. R.
China.
†Electronic Supplementary Information (ESI) available: DSC curves, AIE
curves, CV plots, EL curves, NMR spectra for Si-pTPE, Si-tPE and Si-mTPE.
See DOI: 10.1039/b000000x/
1
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8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 9 of 9
Journal of Materials Chemistry C
View Article Online
DOI: 10.1039/C4TC02631D
New AIEgens containing tetraphenylethene and silole moieties:
tunable intramolecular conjugation, aggregation-induced emission
characteristics, and good device performance
Jie Yang, Ning Sun, Jing Huang, Qianqian Li, Qian Peng, Xi Tang, Yongqiang Dong, Dongge Ma*
and Zhen Li*
p
p
Si
Si
Si-tPE
Si-pTPE
m
m
Si-
Si-tTPE:
Si- TPE:
p
TPE:
= 512 nm,
= 488 nm,
= 7.40 cd/A;
= 8.04 cd/A;
= 1.39 cd/A.
λEL
λEL
λEL
ηC, max
ηC, max
ηC, max
Si
m
= 432 nm,
Si- TPE
m
Three aggregation-induced emission (AIE) luminogens (Si-pTPE, Si-tPE and Si-mTPE) were
successfully obtained by the covalent incorporation of tetraphenylethene to dibenzosilole core,
their emission colors were tuned from green to sky blue even deep blue, through simple
structural modification.