A novel carbazole derivative containing dimesitylboron units: Synthesis, photophysical, aggregation induced emission and electroluminescent properties

Article abstract of DOI:10.1016/j.dyepig.2013.12.017

A novel carbazole derivative containing dimesitylboron groups, 3-dimesitylboryl-9-(4-(3-dimesitylborylcarbazolyl)phenyl)carbazole has been successfully synthesized by introducing two dimesitylboron groups (two electron-acceptors) to 3-position and 3′-position of 1, 4-bis(carbazolyl)benzene (an electron-donor), respectively. The structure of the compound was fully characterized by elemental analysis, mass spectrometry and proton nuclear magnetic resonance spectroscopy methods. The electrochemical and photophysical properties of the compound were studied by electrochemical methods, UV-vis absorption spectroscopy and fluorescence spectroscopy. Our results show that the compound exhibits excellent thermal stability (T _d = 190 °C) and electrochemical stability as well as aggregation induced emission properties. The multi-layered organic light-emitting diodes device was fabricated by using the compound as non-doped emitter. The device shows good electroluminescent performances with the same blue emission color (λ = 478 nm) at different voltages, a turn-on voltage of 3.8 V, a maximum luminance of 2784 cd/m² and a maximum luminance efficiency of 3.25 cd/A.

Full text of DOI:10.1016/j.dyepig.2013.12.017

Accepted Manuscript
A Novel Carbazole Derivative Containing Dimesitylboron Units: Synthesis,
Photophysical, Aggregation Induced Emission and Electroluminescent Properties
Heping Shi, Wenxia Zhang, Xiuqing Dong, Xiaohuan Wu, Yan Wu, Li Fang, Yanqin
Miao, Hua Wang
PII:
S0143-7208(13)00494-4
10.1016/j.dyepig.2013.12.017
DYPI 4214
DOI:
Reference:
To appear in: Dyes and Pigments
Received Date: 10 September 2013
Revised Date: 3 December 2013
Accepted Date: 18 December 2013
Please cite this article as: Shi H, Zhang W, Dong X, Wu X, Wu Y, Fang L, Miao Y, Wang H, A Novel
Carbazole Derivative Containing Dimesitylboron Units: Synthesis, Photophysical, Aggregation
Induced Emission and Electroluminescent Properties, Dyes and Pigments (2014), doi: 10.1016/
j.dyepig.2013.12.017.
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ACCEPTED MANUSCRIPT
A novel carbazole derivative containing dimesitylboron groups with
aggregation induced emission properties was synthesized and utilized as a
highly efficient blue light-emitting material in OLEDs.

ACCEPTED MANUSCRIPT
A Novel Carbazole Derivative Containing Dimesitylboron Units:
Synthesis, Photophysical, Aggregation Induced Emission and
Electroluminescent Properties
a*
Heping Shia*, Wenxia Zhanga, Xiuqing Dong a, Xiaohuan Wua, Yan Wua, Li Fang ,
Yanqin Miaob,c, Hua Wangb,c*
(a) School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, PR
China. E-mail: hepingshi@sxu.edu.cn. Tel.: +86-351-7018094; Fax: +86-351-7011688.
(b) Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan
University of Technology), Ministry of Education, Taiyuan, 030024, China
(c) Research Center of Advanced Materials Science and Technology, Taiyuan University of
Technology, Taiyuan, 030024, China
ABSTRACT
A
novel
carbazole
derivative
containing
dimesitylboron
has
groups,
been
3-dimesitylboryl-9-(4-(3-dimesitylborylcarbazolyl)phenyl)carbazole
successfully synthesized by introducing two dimesitylboron groups (two
electron-acceptors) to 3-position and 3’-position of 1, 4-bis(carbazolyl)benzene (an
electron-donor), respectively. The structure of the compound was fully characterized
by elemental analysis, mass spectrometry and proton nuclear magnetic resonance
spectroscopy methods. The electrochemical and photophysical properties of the
compound were studied by electrochemical methods, UV-vis absorption spectroscopy
and fluorescence spectroscopy. Our results show that the compound exhibits excellent
thermal stability (Td =190 ◦C) and electrochemical stability as well as aggregation
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induced emission properties. The multi-layered organic light-emitting diodes device
was fabricated by using the compound as non-doped emitter. The device shows good
electroluminescent performances with the same blue emission color (λ=478 nm) at
different voltages, a turn-on voltage of 3.8 V, a maximum luminance of 2784 cd/m2
and a maximum luminance efficiency of 3.25 cd/A.
Keywords: Carbazole; Dimesitylboron; Aggregation Induced Emission Properties;
Photophysical Properties; Photoluminescent Properties; Electroluminescent Properties
1. Introduction
Organic light-emitting diodes (OLEDs) have attracted considerable attention
owing to their potential applications in the future flat-panel displays and solid lighting
resources since Tang’s work in the late 1980s [1, 2]. In order to improve the efficiency
of OLEDs, great efforts have been devoted to develop high-performance materials
with desirable properties. At present, many types of high-performance materials have
been produced [3-5]. Among them, carbazole and its derivatives are the most
fashionable ones.
Carbazole is a significant heterocyclic compound with a nitrogen atom as an
electron donor. A large number of carbazole derivatives have been generated through
chemical modification because carbazole can be easily functionalized at 3-, 6-,
9-positions and covalently linked to other molecular groups [6-11]. Carbazole and its
derivatives have high thermal stability and excellent photophysical properties [12-16].
Thus, they are often utilized as organic photoelectronic functional materials [17-20].
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Studies of carbazole and its derivatives have further development in recent years. S.
Grigalevicius and co-workers synthesized and characterized Phenyl or naphthyl-
substituted carbazole derivatives. They prepared the devices using these compounds
as hole-transporting layers. The devices exhibited good overall performance [21]. P. Y.
Stakhira and co-workers synthesized and characterized
a
series of
triphenylamine-substituted carbazoles. These materials showed excellent
hole-transporting properties [22]. Lee and co-workers synthesized two
carbazole-pyrene based fluorophores. These compounds showed excellent
hole-transporting properties [23]. Park and co-workers synthesized a novel series of
new carbazole derivatives, which were excellent deep-blue emitting materials [24].
Zeng and co-workers synthesized a series of starburst carbazole derivatives, and used
these compounds as emitting materials to fabricate the non-doped OLED devices [25].
V. Promarak and co-workers synthesized a series of pyrene-functionalized carbazole
derivatives. They fabricated double-layer and multi-layer devices using these
materials as non-doped emitters. The devices they prepared exhibited good device
performance [26]. R.-H. Lee and co-workers synthesized a series of carbazole
derivatives. They fabricated the non-doped devices using these compounds as
light-emitting layer. The devices exhibited excellent electroluminescent performance
[27].
Triarylboron compounds have attracted a great deal of attention due to their
intriguing electronic and photophysical properties [28, 29]. These excellent properties
derive from the p-π conjugation between the vacant p-orbital on the boron centre with
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the π-orbital of the π-conjugated molecular system [30-34]. At present, many
triarylboron compounds have been synthesized and used in materials chemistry as
nonlinear optical materials and charge-transport and emissive materials in OLEDs and
so on [35-43].
In view of the above-mentioned situation, the molecular design and synthesis of
novel compounds need to be further developed by the structural modification, aiming
to improve the properties and establish the relationship between structures and
properties. In this paper, a novel carbazole derivative containing dimesitylboron
groups,
3-dimesitylboryl-9-(4-(3-dimesitylborylcarbazolyl)phenyl)carbazole(DDCPC), was
synthesized by introducing two dimesitylboron groups (two electron-acceptors) to
3-position and 3’-position of 1, 4- bis(carbazolyl)benzene (an electron-donor),
respectively. The synthetic details are illustrated in Scheme 1. The structure of this
compound was characterized by elemental analysis, 1H NMR, 13C NMR and MS. The
thermal, electrochemical and photophysical properties of DDCPC are also reported.
Finally, DDCPC has been successfully applied to electroluminescent device.
2. Experimental section
2.1 Materials and General Methods
All reagents were used as received from commercial sources without further
purification unless otherwise stated. Solvents were freshly distilled according to the
standard procedures. All reactions were carried out under a nitrogen atmosphere by
using Schlenk techniques. Melting points were determined on an X-5 melting point
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detector. NMR spectra were measured on a Bruker 600 MHz spectromenter. Thermo
gravimetric analysis were performed with a TGA 2050 thermo gravimetric analyzer
under nitrogen atmosphere with a heating rate of 10 °C/min from room temperature to
600 °C. Elemental analyses were performed with an Element Analysis System. Mass
spectra were recorded with the LC-MS system consisted of a Waters 1525 pump and a
Micromass ZQ4000 single quadrupole mass spectrometer detector. Cyclic
voltammetry was acquired on a CHI-600C electrochemical analyzer. The
measurements were performed with a conventional three-electrode configuration
consisting of a glassy carbon working electrode, a platinum-disk auxiliary electrode
and an Ag/AgCl reference electrode. The scan rate was 50 mV/s. UV–vis absorption
spectra were obtained from a Shimadzu UV-2450 absorption spectrophotometer.
Fluorescence spectra were taken on a Shimadzu RF-5301PC fluorescence
spectrometer. Fluorescence quantum yields were determined using a standard
actinometry method; quinine sulphate was used in the actinometer with a known
fluorescence quantum yield of 0.55 in 0.1 M sulfuric acid (excited at 350 nm).
FE-SEM images were studied by a JEOL JSM-67010F field emission scanning
electron microscope. TEM images were studied by a Hitachi H-8100 transmission
electron microscopy. All measurements were performed at room temperature.
2.2 Device fabrication and testing
The multilayer OLEDs were fabricated by vacuum-deposition method. Organic
layers were fabricated by high-vacuum (5×10−4 Pa) thermal evaporation onto a glass
(3 cm×3 cm) substrate precoated with an ITO layer. N, N-bis (naphthalen)-N, N-bis
(phenyl)-benzidine (NPB) was used as the HTL, 4,4'-bis(N-carbazolyl)-1,1'-biphenyl
(CBP) was used as the electron-blocking layer, DDCPC was used as the emitting
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layer, 4,7-diphenyl-1,10-phenanthroline(Bphen) was used as the electron-transport
layer(ETL) and LiF/Al was evaporated as cathode. All organic layers were
sequentially deposited. Thermal deposition rates for organic materials, LiF and Al
were 0.5 Å/s, 0.5 Å/s and 1 Å/s, respectively. The active area of the devices is 9 mm2.
The electroluminescent spectra were measured on a Hitachi MPF-4 fluorescence
spectrometer. The voltage–current density (V–J) characteristics of OLEDs were
recorded on Keithley 2400 Source Meter. The characterization of
brightness–current–voltage (B–I–V) were measured with a 3645 DC power supply
combined with a 1980A spot photometer and were recorded simultaneously. All
measurements were done at room temperature.
2.3 Synthesis of DDCPC
2.3.1 3-bromo-9-(4-(3-bromocarbazolyl)phenyl)carbazole (Compound 1)
A mixture of 3-bromocarbazole (1.934 g, 7.86 mmol), 1, 4-diiodobenzene (1.235
g, 3.74 mmol), 18-crown-6 (0.264 g, 1 mmol), K2CO3 (4.145 g, 30 mmol) and CuI
(0.427 g, 2.24 mmol) was dissolved in DMPU. The reaction mixture was heated to
170 °C for 18 h under a nitrogen atmosphere and then poured into water (600 mL) to
obtain the precipitate. The precipitate was filtered and washed with ethanol (100 mL).
The crude product was purified by column chromatography on silica gel
(CH2Cl2/hexane) to afford the pure white solid (1.191 g, 56% yield). 1H NMR (600
MHz, CDCl3) δ (ppm): 8.25 (d, J = 1.9 Hz, 4H), 7.82 (s, 2H), 7.58 (dd, J = 8.7, 1.9 Hz,
4H), 7.42 (d, J = 8.6Hz, 4H).7.34(s, 4H).
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2.3.2.
3-dimesitylboryl-9-(4-(3-dimesitylborylcarbazolyl)phenyl)carbazole(DDCPC)
1 (1 g, 1.79 mmol) was dissolved in anhydrous THF (50 mL) under a nitrogen
atmosphere and was cooled to -78 °C. Then n-butyllithium (2 mL, 4.47 mmol) was
added. Subsequently, the reaction mixture was left to room temperature for an hour
and then cooled again to -78 °C. Dimesitylboron fluoride (1.2 g, 4.47 mmol) in THF
(20 mL) was dropwisely added over 30 min, and the reaction mixture was warmed
slowly to room temperature. Then it was stirred for 12 h before being quenched with
water (30 mL). The THF was removed under a reduced pressure and the residue was
extracted with CH2Cl2. The combined organic layer was dried over anhydrous MgSO4,
filtered and evaporated under reduced pressure to obtain the crude product. The crude
product was purified by silica-gel column chromatography (CH2Cl2/hexane). Yellow
solid of DDCPC was obtained in 27.5% yield (0.44 g). Mp: 170 °C.1H NMR (600
MHz, CDCl3) δ (ppm): 8.20 (s, 4H), 7.84 (s, 4H), 7.59 (d, J = 8.1 Hz, 4H), 7.48 (d, J
= 8.1 Hz, 4H), 6.72 (m, 10H), 2.27 (s, 12H), 2.02 (s, 24H). 13C NMR (151 MHz,
CDCl3) δ (ppm): 143.87, 141.83, 141.39, 139.50, 131.32, 131.20, 131.10, 129.08,
123.53, 123.25, 112.67, 25.20, and 24.09. MS (m/z): 904.43 (M+); Anal. Calcd for
C66H62B2N2: C, 87.61%; H, 6.91%; N, 3.10%; and Found: C, 86.64%; H, 6.84%; N,
3.08%.
3. Results and discussion
3.1 Synthesis and Characterization
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In
this
work,
the
synthesis
of
3-dimesitylboryl-9-(4-(3-dimesitylborylcarbazolyl)phenyl)carbazole (DDCPC) was
discussed. At first, compound 1 was synthesized via the modified Ullmann reaction.
Then, the final product DDCPC was obtained by reacting compound 1 with n-BuLi,
followed by the addition of dimesitylboron fluoride. The chemical structure of
1
1
compound 1 was confirmed by H NMR whereas DDCPC was confirmed by H
1
NMR, 13C NMR and MS. The H NMR spectrum of DDCPC displays downfield
peaks at 7.00-8.48 ppm which are assigned to the characteristic peaks of carbazole
moieties protons. The downfield peaks at 6.59-6.89 ppm and the upfield peaks at 2.09
and 2.37 are assigned to dimesitylboron moieties protons. The 13C NMR, MS and
elemental analysis are consistent with the desirable structure. Further details are given
in the experimental section. DDCPC is soluble in many common organic solvents
such as CH2Cl2, chloroform, DMF, THF, toluene and DMSO. The thermal property of
DDCPC was investigated by thermogravimetric analysis under a nitrogen atmosphere.
There is only a 5% weight loss at temperature higher than 190°C (Table 1), indicating
that DDCPC has good thermal stability and should be adequate for most
optoelectronic device applications.
3.2. Theoretical Calculation
Theoretical calculations can provide a reasonable qualitative indication of the
excitation and emission properties of a compound [44]. The molecular structure of
DDCPC contains one 1,4-bis(carbazolyl)benzene unit as the core, two dimesitylboron
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units as the terminals. Its geometry at ground state was optimized at
DFT/B3LYP/6-31G (d, p) level using the polarized continuum model (PCM). The
results show that two carbazole moieties are of planar structures and two mesityl
groups form propeller-like conformations originated from their trigonal boron centers.
The highest occupied molecular orbital (HOMO) and the lowest unoccupied
molecular orbital (LUMO) of DDCPC (Fig. 1) were also investigated at
DFT/B3LYP/6-31G (d, p) level using the polarized continuum model (PCM). The
HOMO of DDCPC is localized mainly in the carbazole while the LUMO is in the
dimesitylboron units. Thus, the electronic transition from the ground state to the first
excited state mainly involves intramolecular charge transfer (ICT) from the carbazole
(electron-donor) to the dimesitylboron groups (electron-acceptors). The calculated
HOMO and LUMO energy levels are -5.12 and -1.68 eV, respectively. The
HOMO-LUMO energy gap is 3.44 eV (Table 1). The calculated HOMO and LUMO
levels are higher than the experimental ones and the calculated HOMO-LUMO
energy gap is ca. 0.20 eV larger than that of the optical energy band gap obtained
from UV-vis absorption measurement.
3.3. Photophysical Properties
The UV-vis absorption spectra of DDCPC in various solvents (1.0 × 10−5 M) are
shown in Fig. 2. The absorption data of DDCPC in THF are displayed in Table 1.
DDCPC exhibits one absorption band at 280-320 nm corresponding to the π-π*
electronic transitions. The low-energy broad band at 320-380 nm is assigned to ICT
from the carbazole core to dimesitylboron terminals and shows almost identical
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maxima absorption in the different solvents, meaning the slightly solvent-dependence
[45]. The result indicates that solvent polarity does not affect the structural and
electronic characteristics of the ground state of DDCPC significantly. Moreover, the
optical energy band gap calculated from the absorption band edges of the UV-vis
absorption spectra is approximately 3.24 eV.
Fig. 3 depicts the fluorescence spectra of DDCPC in various solvents (1.0 × 10−5
M). The fluorescence data in THF is summarized in Table 1. The absorption spectrum
of DDCPC shows slight solvatochromism effect whereas the fluorescence emission
shows a significant solvatochromism effect. With the polarity increasing of the
solvents, a bathochromic shift of 44 nm ranging from 368 nm (in hexane) to 412 nm
(in DMSO) was observed. Such a distinct solvatochromism indicates that
intramolecular charge transfer from the carbazole core to two dimesitylboron
terminals takes place during the excitation process. The fluorescence quantum yield
(Φ) of DDCPC in various solvents were measured by using quinine bisulfate in 0.1 M
sulfuric acid as the standard [46]. The fluorescence quantum yield data in THF
solvent is summarized in Table 1. The solid fluorescence spectrum of DDCPC was
obtained by measuring its solid film. The spectrum is shown in Electronic
Supplementary Information (Fig. S1). The spectrum shows the emission maximum of
DDCPC is at 480 nm in the solid film state, demonstrating that it can emit blue light.
The photoluminescent properties of DDCPC in solutions and solid film state indicate
it could be used as an excellent optoelectronic material with blue light emission in
OLEDs.
3.4 Aggregation Induced Emission (AIE) Properties
The aggregation induced emission (AIE) behavior was investigated by
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monitoring the change in PL intensity with the addition of water ratio in a THF–water
solvent mixture. Here, THF acts as the solvent and water acts as the non-solvent [47].
There is a dramatic change of the fluorescence spectra of DDCPC from the THF
solution to the THF–water mixture (Fig.4). With the increasing proportion of water,
the emission intensity and wavelength show a slight decrease and red shift,
respectively, due to the increasing polarity of the system. When the water content is
higher than 50vol%, nano-particles begin to form and the purple emission band
centered at 402 nm gradually “turns-off’’, along with the blue emission band at 493
nm rapidly “turning-on’’, which suggests that molecules begin to aggregate in the
solvent mixture with this composition. The nano-particles of DDCPC were prepared
by the precipitation method in the absence of surfactants. DDCPC must aggregate
into nano-particles in the THF–water mixture because water is a non-solvent for
DDCPC in THF. The shape of nano-particles was investigated by FE-SEM and TEM.
Fig. 5 shows FE-SEM images of nano-particles from THF-water (1: 9) mixture
solution onto a conductive tape substrate, which shows a large number of discrete
nano-particles. Besides, nano-particles with a diameter of about 30-80 nm are clearly
observed by TEM images (the inset of Fig.5), which are in good agreement with those
shown in the FE-SEM images. In addition, to date such a ratiometric fluorescence
change with a large red-shift of 90 nm in an ICT compound has rarely been reported.
Furthermore, this AIE active molecule can be used as luminescent materials in
OLEDs.
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3.5 Electrochemical Properties
The electrochemical properties of DDCPC were investigated by cyclic
voltammetry (CV) with Ag/AgCl as the reference electrode. The measurement was
conducted in 1.0 × 10−3 M DDCPC in acetonitrile containing 0.10 M
tetrabutylammonium perchlorate as the supporting electrolyte under a nitrogen
atmosphere. The cyclic voltammogram (CV) of DDCPC is shown in Fig. S2 (ESI).
The CV curves remain unchanged under multiple successive potential scans,
indicating its excellent stability against electrochemical oxidation. The HOMO energy
level can be calculated with the empirical equation HOMO = - (Eox + 4.40) eV, where
Eox is the onset oxidation potential [48]. The Eox is 0.85 eV and the HOMO energy
level of DDCPC is -5.25 eV. The energy band gap (Eg) was estimated to be 3.24 eV
by the absorption edges of the UV-vis spectra. The LUMO energy level of DDCPC is
-2.01 eV, which was calculated from the HOMO energy level and Eg (ELUMO = EHOMO
+ Eg). The results are summarized in Table 1. The HOMO energy level of DDCPC is
lower than the work functions of indium tin oxide (ITO) electrodes, implying its
potential application as hole- transporting materials in OLEDs [49].
3.6 Electroluminescent property
In order to demonstrate the potential application of DDCPC as luminescent
material in device, the multi-layer device (Device M) with the structure of indium tin
oxide (ITO) / N,N’-di-1-naphthyl-N,N’-diphenylbenzidine (NPB) (40 nm) /
4,4’-bis(N-carbazol-yl)-1,10-biphenyl (CBP) (10 nm)
/
DDCPC (20 nm)
/4,7-diphenyl-1,10-phenanthroline (Bphen) (40 nm) / LiF (1 nm) / Al (180 nm) was
fabricated by vacuum deposition, wherein NPB and Bphen were used as the
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hole-transporting layer and the electron-transporting layer, respectively; CBP and
DDCPC served as the electron-blocking layer and the emitting layer, respectively.
The multi-layer device (Device M) emits an excellent blue light (λ=478 nm) with CIE
coordinates (0.23, 0.35). The EL spectra of the device keep unchanged when the
driving voltage increases from 3.6 to 14 V and the EL spectra are identical to its PL
spectrum of thin film. The multi-layer device (Device M) exhibits good performance
with a turn-on voltage of 3.8 V, a maximum luminance of 2784 cd m-2 and a
maximum luminescent efficiency of 3.25 cd/A (Table 2). The current
density–voltage–luminance curve and luminance efficiency-current density curve of
the device are shown in Fig. 6 and Fig.7, respectively. It should be pointed out that the
electroluminescent performances were obtained in a non-optimized test device under
ordinary laboratory conditions. The device performances may be further improved by
an optimization of the layer thicknesses and processing conditions. Studies on the
improvement of the device performances are currently underway.
4. Conclusions
In summary,
a
novel acceptor-π-donor-π-acceptor type compound,
3-dimesitylboryl-9-(4-(3-dimesitylborylcarbazolyl)phenyl)carbazole(DDCPC), has
been successfully synthesized and characterized by elemental analysis, NMR, MS and
thermogravimetric analysis. The electrochemical and photophysical properties of
DDCPC were studied by combination of experimental and theoretical methods. Our
results show that DDCPC exhibits excellent thermal stability (Td =190 ◦C) and
13

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electrochemical stability as well as aggregation induced emission (AIE) properties.
Furthermore, the multi-layer electroluminescent device using DDCPC as
light-emitting layer is fabricated. The multi-layer device (Device M) emits an
excellent blue light (λ=478 nm) with CIE coordinates (0.23, 0.35) and shows good
electroluminescent performances with a turn-on voltage of 3.8 V, a maximum
luminance efficiency of 3.25 cd A-1 and a maximum luminance of 2784 cd m-2. All
results indicate DDCPC is a promising material for the construction of efficient
non-doped blue OLEDs.
Acknowledgements
This work was supported by Natural Science Foundation of Shanxi Province (No
2013011013-1), Programs of Higher Education Institutions in Shanxi Province (No
2012005), Shanxi Scholarship Council of China (Grant No. 2012-006), Shanxi
Science and Technology Department (Grant No. 20100321085) and Fund of Key
Laboratory of Optoelectronic Materials Chemistry and Physics, Chinese Academy of
Sciences (No 2008DP173016). All the calculations have been performed with the
advanced computing facilities of supercomputing centre of computer network
information centre of Chinese Academy of Sciences. All the authors express their
deep thanks.
Appendix A. Electronic Supplementary Information
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Captions for Table, Figures and Scheme
Table 1. Physical properties of compound DDCPC
Table 2. Electroluminescent characteristics of Device M
Fig. 1. HOMO and LUMO diagrams of DDCPC
Fig. 2. UV-vis absorption spectra of DDCPC in different solvents.
Fig. 3. Fluorescence emission spectra of DDCPC in different solvents. The excitation
wavelength is 350 nm.
Fig. 4. Fluorescence spectra of DDCPC (5 mM) in the THF–water mixture with
different fractions of water (fw). Excited at 350 nm.
Fig. 5. FE-SEM and TEM (the inset) images of the nanoparticles prepared in the
THF–water(1: 9) mixture.
Fig. 6. Current density–voltage–luminance curves of the Device M
Fig. 7. Current density-luminance efficiency curve of the device
Scheme 1 Synthetic routes of DDCPC.
19

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Table 1. Physical properties of compound DDCPC
d
f
g
Φc
a
a
b
Com.
Td
(oC)
HOMO/
LUMOe
(eV)
Eg
(eV)
HOMO/
LUMOg
(eV)
Eg
(eV)
λabs
(nm)
λem
λem
(nm) (nm)
DDCPC 293/348
383
480 0.22 190
-5.25/-2.01 3.24 -5.12/-1.68 3.44
a
b
c
Measured in THF. Measured in film. Measured in THF with quinine sulfate as a standard. d Obtained from
e
TGA.
Obtained from CV in CH3CN/n-Bu4NClO4 and estimated from HOMO= -(4.44+Eoxonset);
LUMO=HOMO+Eg. fCalculated from the absorption edge, Eg=1240/λonset. g Obtained from DFT calculation.
Table 2. Electroluminescent characteristics of Device M
L,max (cd A−1)
3.25
Device
VON (V)
3.8
Lmax (cd m−2)
λ
EL (nm)
478
η
Device M
2784
Von = turn-on voltage at 1 cd m−2, Lmax = maximum luminance, ηL,max = maximum luminance efficiency
20

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HOMO
LUMO
Fig. 1. HOMO and LUMO diagrams of DDCPC

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0.8
0.6
0.4
0.2
0.0
Hex
THF
Chloroform
CH CN
3
DMSO
275
300
325
350
375
400
Wavelength/nm
Fig.2. UV–vis spectra of DDCPC in different polar solvents.

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1.0
0.8
0.6
0.4
0.2
0.0
Hex
THF
Chloroform
CH CN
3
DMSO
350
400
450
500
550
600
Wavelength/nm
Fig. 3. Fluorescence emission spectra of DDCPC in different solvents. The excitation
wavelength is 350 nm

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160
140
120
100
80
fw(vol%)
10
20
30
40
45
50
55
60
65
70
60
75
80
40
85
20
90
95
0
-20
350
400
450
500
550
600
650
Wavelength/nm
Fig. 4. Fluorescence spectra of DDCPC (5 mM) in the THF–water
mixture with different fractions of water (fw). Excited at 350 nm.

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Fig. 5 FE-SEM and TEM (the inset) images of the nanoparticles prepared
in the THF–water(1: 9) mixture.

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Device M
102
101
100
10-1
10-2
10-3
10-4
105
104
103
102
101
100
2
4
6
8
Voltage (V)
Fig. 6. Current density–voltage–luminance curves of the Device M

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10
Device M
1
0.1
0.1
1
10
100
Current Density ( mA/cm2)
Fig. 7. Current density-luminance efficiency curve of the device

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B
Br
I
I
F
B
N
N
N
Br
N
N
H
Br
B
Scheme 1 Synthetic routes of DDCPC.