Synthesis and properties of blue luminescent bipolar materials constructed with carbazole and anthracene units with 4-cyanophenyl substitute at the 9-position of the carbazole unit

Article abstract of DOI:10.1002/bio.3452

With carbazole and p-cyanobromobenzene as raw materials, 4-(3,6-di (anthracen-9-yl)-9H-carbazol-9-yl)benzonitrile (DACB) and 4-(3,6-bis(anthracene -9-ylethynyl)-9H-carbazol-9-yl)benzonitrile (BACB) were synthesized through the Suzuki coupling reaction and

Full text of DOI:10.1002/bio.3452

Received: 23 October 2017
DOI: 10.1002/bio.3452
Revised: 8 December 2017
Accepted: 12 December 2017
R E S E A R C H A R T I C L E
Synthesis and properties of blue luminescent bipolar materials
constructed with carbazole and anthracene units with
4
‐cyanophenyl substitute at the 9‐position of the carbazole unit
1
1
1
1
2
2
|
|
|
|
|
Pengbo Xie
Ningning Yuan
Shanji Li
Ying Ouyang
Yongju Zhu
Hui Liang
1
Petrochemical Engineering Department of
Guangzhou Institute of Technology,
Guangzhou, China
Abstract
With carbazole and p‐cyanobromobenzene as raw materials, 4‐(3,6‐di (anthracen‐9‐yl)‐9H‐
carbazol‐9‐yl)benzonitrile (DACB) and 4‐(3,6‐bis(anthracene ‐9‐ylethynyl)‐9H‐carbazol‐9‐yl)
benzonitrile (BACB) were synthesized through the Suzuki coupling reaction and the Sonogashira
2
School of Chemistry and Chemical
Engineering, Sun Yat‐sen University,
Guangzhou, China
1
coupling reaction, respectively. These structures were characterized using H nuclear magnetic
Correspondence
resonance (NMR), elemental analysis and mass spectrometry. Their thermal properties, ultravio-
let–visible (UV‐vis) absorption, fluorescence emission, fluorescence quantum yields and electro-
chemical properties were also investigated systematically. In addition, a electroluminescence
Shanji Li, Petrochemical Engineering
Department of Guangzhou Institute of
Technology, Guangzhou 510725, China.
Email: hnlsj2004@163.com
(EL) device was made with BACB as the emitting layer and performance of the EL device was
Funding information
studied. Results showed that: (1) the temperature points with 5% and 10% of DACB weight loss
were 443°C and 461°C, respectively, and were 475°C and 506°C with BACB weight loss of 5%
and 10%, respectively. When the temperature was 50−300°C, no significantly thermal transition
was observed which suggested that they had excellent thermal stability. (2) DACB and BACB had
single emission peaks at 415 nm, and 479 nm with fluorescence quantum yields of 0.61 and 0.87,
respectively, indicating that both compounds could emit strong blue light. (3) According to elec-
trochemical measurement on BACB and DACB, their gaps were 3.07 eV and 2.76 eV, respec-
tively, which further showed that these two compounds were very stable and acted as efficient
blue light materials. (4) The turn‐on voltage of the device was 5 V, and the device emitted dark
blue light with Commission Internationale de L'Eclairage (CIE) coordinates of (0.157, 0.079).
Guangzhou Institute of Technology Key
Projects Foundation, Grant/Award Number:
ZSH201609; Guangzhou City Education Sys-
tem Innovative Academic Team Foundation,
Grant/Award Number: 1201610020
KEYWORDS
bipolar materials, blue luminescent, quantum yield
1
|
INTRODUCTION
prepare green and red devices. Therefore, blue light materials are
[
1]
always the focus in studies on organic light‐emitting materials.
Red, green, and blue colour materials are the basis for full colour dis-
play, in which blue light material itself cannot only be used as a light‐
emitting layer to prepare blue‐ray organic light‐emitting diodes
However, research progress on blue light materials is still slower
than that of green and red materials, because blue light materials that
[
2]
exhibit high yield and good stability are still very challenging due to
(
OLEDs), but also be used to dope other luminescent materials to
the wider gap (3.0 eV) required by stable and efficient blue light mate-
[
3]
rials, making blue light emission more difficult. Therefore, in order to
produce efficient blue light devices, it is especially important to pre-
pare major blue luminescent materials with superior properties. This
Abbreviations used: CIE, Commission Internationale de L'Eclairage; CV, cyclic
voltammetry; DPA, 9,10‐diphenylanthracene; DSC, differential scanning
calorimetry; EL, electroluminescence; HOMO, highest occupied molecular
orbital; HTL, hole transporting layer; LUMO, lowest unoccupied molecular
orbital; NMR, nuclear magnetic resonance; OLED, organic light‐emitting
[
4,5]
focus has attracted the interest of researchers
and become the
[15]
[
6–14]
focus of the OLED industry and research.
Since Pope et al.
observed the faint blue light for the first time when hundreds of volts
of direct current were added on anthracene single crystal, scientists
have continuously studied to improve their brightness and yield, and
diodes;
PL,
photoluminescence;
RE,
reference
electrode;
TGA,
thermogravimetric analysis; UV, ultraviolet.
Luminescence. 2018;1–7.
wileyonlinelibrary.com/journal/bio
Copyright © 2018 John Wiley & Sons, Ltd.
1

2
XIE ET AL.
prepare blue luminescent materials with good performance and good
(96%), n‐butyllithium (1.6
M
in toluene), 2‐methyl−3‐butyn‐2‐ol
[
15–19]
results.
Anthracene intermolecular crystals are easy to form
(98%), cesium carbonate (99.5%), 4‐bromobenonitrile (98%), and
tetrabutylammonium hexafluorophosphate were purchased from
Acros Organic and used as received. Tetrakis(triphenylphosphine)pal-
ladium(0) (99.8%), CuI (98%), Alfa Aesar; 1,1´‐bis(diphenylphosphino)
ferrocene (DPPF, 99%), Strem Chemicals. anthracen‐9‐ylboronic
because of the flat structure of the anthracene molecule. However,
the performance of blue light material anthracene and its derivatives
is still much worse than that of red and green lights, which greatly
reduce the practical value of anthracene in OLEDs.
[
27]
[28]
Because of carbazole's strong absorption in the short wavelength
range, its energy band gap of around 3.2 eV and its unique optical
properties, carbazole and its derivatives as hole transport materials
have been widely used for small molecule and polymer blue
acid
and 9‐ethynylanthracene
were synthesized according to
the literature procedures. Other reagents were all purified with stan-
dard methods if needed.
[
20–23]
OLED.
However, the size of small molecule light materials from
2
.2
|
Characterization
carbazole derivatives is small with poor thermal stability and the quan-
tum yield of polymer materials is still low, thus their applications have
been limited. In general, due to their chemical structure and energy
level, most organic semiconductor unipolar materials tend to transmit
a carrier (electron or hole) and have lower transmission capacity for
another carrier. In the single layer devices made from unipolar mate-
rials, the electron concentration and hole concentration are unbal-
anced, resulting in decreased performance and reduced device life
due to movement of the light‐emitting layer to the electrode/organic
Melting points were measured on a SGW X‐4 micro melting point
1
apparatus. H‐NMR spectra were recorded on a Mercury‐Plus 300
3
NMR spectrometer (Varian) in CDCl with tetramethylsilane as an
internal standard. Chemical shifts were reported in ppm relative to
the internal standard tetramethylsilane. Elemental analyses were car-
ried out on a Vario EL Elemental Analyzer (Elementar). EI‐mass mea-
surements were carried out on
a DSQ EI‐mass spectrometer
(Thermo). UV‐vis absorption spectra were recorded on a TU‐1901
spectrophotometer. Emission spectra were recorded on a Perkin‐Elmer
LS 55 fluorescence spectrophotometer. Differential scanning calorime-
try (DSC) measurements were carried out on a Netzsch DSC‐204 dif-
[
24]
layer interface.
While, as light‐emitting layer, ambipolar transmis-
sion materials can also improve matching of electron and hole to
[
25]
obtain single layer devices with high brightness and high yields.
Therefore, more and more attention has been paid to ambipolar trans-
mission materials with effectively balanced carriers in devices to
2
ferential scanning calorimeter (heating rate: 10°C/min; atmos.: N ,
20.00 ml/min). Thermogravimetric analyses (TGA) were recorded on
[26]
improve their lighting yield and stability.
a Perkin‐Elmer TGS‐2 thermogravimeter (heating rate: 20°C/min;
To date, mobility of electrons and holes in all reported ambipolar
atmos.: N
formed on a PPS‐268A potentiostat with a glassy carbon working elec-
trode and a Ag/AgNO (0.1 M in acetonitrile) reference electrode (scan
2
, 45.00 ml/min). Electrochemical experiments were per-
materials with donor–acceptor structures have a difference of one to
[27−30]
two orders of magnitude without a good balance.
Although
3
–
1
abundant numbers and types of ambipolar transmission materials have
been reported, there are very limited materials reported with excellent
performance. Therefore, the development of high‐performance
ambipolar light‐emitting materials has become the focus of studies
rate: 100 mV sec ). Dichloromethane was used as the solvent, and
tetra‐n‐butylammonium hexafluorophosphate (0.1 M) was used as
the supporting electrolyte. The characteristics of voltage–current–
luminance was recorded by Keithley 2400 SourceMeter (Keithley,
USA) and corrected silicon photodiode, The electroluminescence spec-
tra (EL) were recorded using a InstaspecIV CCD system (Oriel, USA).
[
31−34]
and investigation.
In this study, p‐cyanophenyl with strong electronic absorbing capa-
bility was introduced into the nitrogen on carbazole position 9, followed
by the introduction of a 9‐anthracene group on the carbazoole positions
of 3 and 6, to synthesize the conjugated carbazole–anthracene compli-
cated structure compound 4‐(3,6‐bis (anthracene ‐9‐ylethynyl)‐9H‐
carbazol‐9‐yl)benzonitrile (BACB) with acetylene to connect tcarbazole
and anthracene and the complicated structure compound 4‐(3,6‐
di(anthracene‐ 9‐yl)‐9H‐carbazol‐9‐yl)benzonitrile (DACB) with the
introduced 9‐anthryl to connect the carbazole and anthracene directly.
These thermal and optical properties were studied to obtain ambipolar
blue light‐emitting materials with excellent performance.
2
.3
|
Preparation of blue luminescent bipolar
materials
2.3.1
|
Synthesis of compound 4‐(9H‐carbazol‐9‐yl)
[29]
benzonitrile (CBN)
3 4
In the glove box, DPPF (400 mg, 0.72 mmol), Pd(PPh ) (346.5 mg and
0.3 mmol) and newly distilled toluene (15 ml) after 30 min of oxygen
removal with the flux of nitrogen 30 min were added into a 100 ml sin-
gle‐neck bottle. After 30 min of stirring, carbazole (2.004 g, 12 mmol), p‐
2 3
cyanobenzyl bromide (2.715 g, 15 mmol), Cs CO (4.890 g, 15 mmol)
and toluene (55 ml) were added, sealed, moved out from the glove
box and reacted for 24 h in an oil bath at 100°C under nitrogen protec-
tion. After the reaction, the mixture was filtered and the filter residual
was washed three times with ethyl acetate. Organic phases were com-
bined together, washed twice with both distilled water and saturated
salt water, and dried with sodium sulfate overnight. The solvent was
removed with a rotary vapour. The solid was dissolved with a small num-
ber of tetrahydroflurans (THF) under heating, recrystallized with the
dropwise addition of anhydrous methanol. After filtration, the crystal
2
2
|
EXPERIMENTAL
.1
|
Materials and methods
Iodic acid (HIO
3
), ≥99.5%, Shanghai Xinliang Chemical Reagent Co
), CP, Sinopharm Chemical Reagent Co
Ltd; triphenylphosphine (PPh
3
Ltd; KI, >99.5%, Tianjin Damao Chemical Reagent Factory;
triisopropyl borate (98%), J&K; 9‐bromoanthracene (96%), carbazole

XIE ET AL.
3
was washed three times with methanol to obtain a white crystal (2.95 g)
and refilled with N
2
for three times. A mixture of 90 ml freshly distilled
1
with a yield of 92% and a melting point of 176–177°C. H‐NMR
toluene, 30 ml of freshly distilled methanol, and 15 ml of 2 M aqueous
solution of K CO , degassed by bubbling N under stirred for 30 min,
was added to the flask via a syringe. The resulting mixture was stirred
under N for 48 h at 50°C. After reaction, the reaction mixture was fil-
(
300 MHz, CDCl
3
): d(ppm) 8.14 (d,J = 7.8 Hz, 2H), 7.91 (d,J = 8.Hz,
2
3
2
2
H), 7.74 (d,J = 8.7 Hz, 2H), 7.40−7.48 (m, 4H), 7.30−7.37 (m, 2H).
2
|
Synthesis of compound 4‐(3,6‐diiodo‐9H‐carbazol‐
tered. The obtained precipitates were washed with water and toluene
successively, then dissolved withTHF, and filtered through a short col-
umn of silica gel to remove the catalyst. The crude product was purified
2
9
.3.2
‐yl) benzonitrile (DICBN)
A mixture of CBN (2.95 g, 11 mmol), KI (2.74 g, 14.5 mmol), and HIO
3
3
by recrystallization from THF/CH OH. Yellow solid 1.37 g; yield 74%.
(
3.53 g, 16.5 mmol) in Acetic Acid (AcOH) (40 ml) was stirred at 115°C
1
mp 357−359°C. H NMR: δ 8.50 (s, 2H), 8.16 (s, 2H), 7.98–8.08 (m,
for 30 min. Then the mixture was filtered when it was warm. The
obtained precipitates were washed with AcOH. The crude product
8
H), 7.70−7.77 (m, 6H), 7.54 (d, J = 8.4 Hz, 2H), 7.44 (t, J = 7.5 Hz,
H), 7.32 (t, J = 7.5 Hz, 4H). Anal. calcd.: C16 21IO, C, 90.94; H, 4.55;
4
H
3
was purified by recrystallization from THF/CH OH. Yellow solid,
1
N, 4.51; found: C, 90.79; H, 4.82; N, 4.27. EI MS m/z calcd.: 620.23;
4
.51 g; yield 79.0%. mp. 249–250°C. H‐NMR: δ 8.39 (s, 2H), 7.92
found: 620.
(
d, J = 8.4 Hz, 2H), 7.68 (t, J = 8.4 Hz, 4H), 7.18 (d, J = 8.4 Hz, 2H). Anal.
calcd: C19 , C, 43.88; H, 1.94; I, 48.80; N, 5.39; found: EI MS
m/z 519.89; found: 520.
10 2 2
H I N
3
|
RESULTS AND DISCUSSION
2
.3.3
|
Synthesis of compound BACB
All compounds were stable at atmospheric temperature and pressure
and were soluble in common organic solvents. Their spectroscopic data
were in good agreement with the proposed structures in Scheme 1
and Scheme 2.
To a two‐necked 250 ml flask, 0.416 g (0.8 mmol) of DICBN, 0.45 g
2.23 mmol) of 9‐ethynylanthracene, 12.5 mg of Pd(PPh Cl
5.3 mg of CuI, and 23.2 mg of triphenylphosphine were added. The
(
3
)
2
2
,
1
2
flask was vacuumed and refilled with N . This process was repeated
three times. A mixture of 60 ml freshly distilled toluene and 20 ml of
freshly distilled Et N, degassed by bubbling N under stirring for
0 min, was added to the flask. The resulting mixture was stirred for
h at room temperature, then overnight at 80°C. After the reaction,
3
.1
|
Structural description
3
2
The synthetic routes of all compounds are shown in Scheme 1 and
3
1
1
Scheme 2. The compounds were characterized by H‐NMR, ESI‐MS,
TGA, DSC and UV‐vis analysis.
the mixture was cooled and filtered. The filtrate was washed with
water, and saturated NaCl solution successively, dried with anhydrous
3.2
|
Thermal properties
Na
rotary evaporation. The crude product was purified by recrystallization
from THF/CH OH after column chromatography on silica gel with
2
SO
4
, then filtered. The solvent in the filtrate was removed by
After the sample was dried for 12 h at 40°C under vacuum in advance,
its thermogravimetry (TG) and DSC experiments were conducted in a
3
petroleum/THF (v/v = 4/1). Yellow solid 0.358 g; yield 67%. mp
2
N atmosphere with a TG heating rate of 20°C/min, DSC heating rate
1
3
2
8
28−329°C. H‐NMR: δ 8.76 (d, J = 8.7 Hz, 4H), 8.65 (s, 2H), 8.45 (s,
H), 8.05 (d, J = 8.4 Hz, 4H), 8.00 (d, J = 8.1 Hz, 2H), 7.89 (d, J =
.4 Hz, 2H), 7.83 (d, J = 8.4 Hz, 2H), 7.61−7.69 (m, 4H), 7.50−7.58
of 10°C/min, TG test temperature range of 50−700°C and DSC test
temperature range of 50−300°C. TG and DSC results for DACB and
BACB are shown in Figures 1 and 2, respectively.
(
m, 6H). Anal. calcd: C16H21IO, C, 91.59; H, 4.22; N, 4.19; found: C,
As shown in Figure 1, in N
around 410°C with 5% weight loss at 443°C and 10% weight loss at
61°C. BACB started to lose weight at around 260°C with 5% weight
2
, DACB started to lose weight at
9
1.71; H, 4.37; N, 3.98. EI MS m/z calcd.: 668.23; found: 668.
4
2
.3.4
|
Synthesis of compound DACB
loss at 475°C and 10% of weight loss at 506°C. The weight loss of
BACB at 220−320°C might be due to evaporation of solvent or volatile
impurities in its crystal lattice. According to their thermogravimetric
analysis, these two compounds both had high thermal stability and
To a 250 ml flask, 1.56 g (3 mmol) of DICBN, 2 g (9 mmol) of anthracen‐
‐ylboronic acid, 346.5 mg (0.3 mmol) of Pd(PPh , and 157.2 mg
0.6 mmol) of triphenyl‐phosphine were added. The flask was vacuated
9
3 4
)
(
SCHEME 1 Synthetic route of CBN and DICBN

4
XIE ET AL.
SCHEME 2 Synthetic route of BACB and DACB
the thermal decomposition temperature of DACB without an alkynyl
group was higher than that of BACB with an alkynyl group, probably
due to the instability of alkynyl compounds.
As shown in Figure 2, there were not significant heat changes for
DACB and BACB at 50−300°C, indicating that they had good thermal
stability. On melting point apparatus, their melting points was deter-
mined as 357−359°C and 328−330°C.
Therefore, both DACB and BACB had excellent thermal stabilities
according to their TG and DSC results.
3
.3
|
Photophysical properties
At room temperature, with tetrahydrofuran as solvent, ultraviolet
absorption spectra of DACB and BACB solution are shown in Figure 3.
According to the ultraviolet absorption spectra in THF solution,
both compounds had four peaks within 320−450 nm at 387 nm,
368 nm, 349 nm and 334 nm for DACB, and at 434 nm, 409 nm,
FIGURE 1 TG curves for DACB and BACB
FIGURE 2 DSC curves for DACB and BACB

XIE ET AL.
5
TABLE 1 Fluorescence quantum yields of DACB and BACB in THF
Fluorescence
λexmax Adsorption Fluorescence quantum yield
(nm)
(A)
strength (I)
f
(Φ )
The standard 373
0.0355
9168
6255
6097
0.90
0.61
0.87
DACB
BACB
367
409
0.0349
0.0237
quantum yield of BACB with the introduction of an alkynyl group
was increased significantly over that of DACB, indicating that the
proper introduction of an alkynyl group could increase the π‐electron
conjugated system in the molecule and also increase the fluorescence
quantum yield.
3
.4
|
Electrochemical properties
Cyclic voltammetry (CV) was done on a PS‐268A electrochemical mea-
suring instrument (Beijing Middle Corrosion Protection Engineering
Technology Ltd) with a three‐electrode system and a glassy carbon
electrode as the working electrode, Ag/Ag+ (0.1 M acetonitrile solu-
tion) as the reference electrode (RE), platinum electrode as the auxil-
iary electrode (AE), a scanning rate of 20 mV/sec, dichloromethane
as solvent, and tetrabutylammonium hexafluorophosphate (0.1 M) as
the supporting electrolyte. After the analysis on electrochemical prop-
erties of the synthesized materials, their highest occupied molecular
orbital (HOMO) and lowest unoccupied molecular orbital (LUMO)
energy levels could be calculated according to the following
FIGURE 3 UV absorption spectra of DACB and BACB
3
88 nm and 367 nm for BACB, respectively. DACB had the character-
[30]
istic absorption peaks of the anthracene group
while UV absorption
peaks of BACB with an alkynyl group had a relative red shift.
Figure 4 shows the fluorescence spectra of DACB and BACB solu-
tion in THF at room temperature.
As shown in Figure 4, emission spectra of both DACB and BACB
were single peaks with shoulders, in which the maximum emission
wavelength (λmax) of DACB was 415 nm while the λmax of BACB
was 479 nm. Similar to their corresponding UV absorption spectra,
fluorescent emission peaks of BACB had a red shift of 64 nm
compared with that of DACB because the introduction of alkynyl
molecules resulted in an increase in the π‐electron conjugated sys-
tem. Meanwhile, 9,10‐diphenylanthracene (DPA) was chosen as the
[
32,33]:
formula
EHOMO ¼ −4:71−Epa ðonsetÞ; ELUMO ¼ Eg−∣EHOMO∣; Eg ¼ 1240=λabs
where Epa (onset) is the initial oxidation potential, ELUMO is the LUMO
energy level, Eg is the band between HOMO and LUMO, λabs is the
intersection point of the tangential curve on the direction of UV‐vis
adsorption wave and the baseline. The results are shown in Figure 5.
After the starting oxidation potentials of DACB and BACB were
obtained as shown in Figure 5, with the intersection point of tangential
curve on the direction of UV‐vis adsorption wave and the baseline, the
above‐mentioned formula could be used to calculate their HOMO and
LUMO energy levels as well as the gaps between them, and the results
are shown in Table 2.
[
31]
standard (Φf(cyclohexane) = 0.9)
to determine fluorescence quantum
yields of DACB and BACB and the results are listed in Table 1.
As listed in Table 1, these three compounds all had fluorescence
quantum yields above the average, in which the fluorescence quantum
yield of BACB was similar to that of the standard DPA. Through com-
parison, for compounds with similar structures, the fluorescence
As listed in Table 2, the energy barrier between the LUMO energy
level (–2.37) of DACB and Mg:Ag cathode (−3.7 eV) was small and in
favour of electronic injection, therefore, DACB was more suitable as
a blue light material for electronic transmission, probably because the
alkynyl group in BACB might enhance the conjugation and flatness of
the molecule.
3
.5
|
Electroluminescent properties
Firstly,
N,N´‐di‐[(1‐naphthyl)‐N,N´‐diphenyl]‐1,1´‐biphenyl)‐4,4´‐
diamine (NPB) and BACB were used as the hole transporting layer
HTL) and luminescent layer respectively, and the organic layers and
(
the top cathode of Al/LiF were successively vacuum deposited onto
an indium–tin oxide (ITO)‐coated glass substrate to fabricate the elec-
troluminescence (EL) device. The EL device structure is ITO/NPB
FIGURE 4 Fluorescence emission spectra of DACB and BACB

6
XIE ET AL.
FIGURE 5 Cyclic voltammetry curves of DACB and BACB
TABLE 2 HOMO and LUMO energy levels of DACB and BACB
Epa(onset) (eV)
Eg (eV)
EHOMO (eV)
E
LUMO (eV)
DACB
BACB
0.73
0.51
3.07
2.76
−5.44
−5.22
−2.37
2.46
FIGURE
8
The luminance–voltage–current density curves of the
device
FIGURE 6 The structure of the EL device
As shown in Figure 7, the device emits dark blue light with λmax at
476 nm accompanied by a weak shoulder peak at 487 nm at a voltage
of 10 V. By contrast, the electroluminescent spectra (EL) of the device
are similar to the photoluminescence spectra (PL), and the maximum
wavelength (476 nm) of electroluminescence is only 3 nm less than
the maximum wavelength (479 nm) of photoluminescence, indicating
that the light from the device is mainly produced from the compound
BACB.
Finally, the luminance–voltage–current density curves of the ITO/
NPB/BACB/TPBi/LiF/Al device were recorded and displayed in
Figure 8.
As shown in Figure 8, the turn‐on voltage, which is defined as the
2
voltage at which the luminance is 1 cd/m , was measured and found to
be 5 V. At the same time, it was found that the luminance increased
with increasing injection current as well as bias voltage. At the driven
2
voltage of 10 V, the maximum luminance of 2300 cd/m , the current
2
densities of 200 mA/cm and the maximum luminance efficiency of
6.55 cd/A were obtained, respectively. The device emits dark blue light
FIGURE 7 El spectrum and PL spectrum of the device
40 nm)/BACB (20 nm)/TPBi (20 nm)/LiF (0.5 nm)/Al (95 nm) and is
with Commission Internationale de L'Eclairage (CIE) coordinates of
(
0.157, 0.079).
(
shown in Figure 6.
Secondly, the electroluminescence (EL) spectrum and
photoluminescence (PL) spectrum of ITO/NPB (40 nm)/BACB
|
4
CONCLUSION
(
20 nm)/TPBi (20 nm)/LiF (0.5 nm)/Al (95 nm) device were researched
With carbazole as the raw material, DACB and BACB were synthesized
through the Suzuki coupling and Sonogashira coupling reactions, with
and the results are shown in Figure 7.

XIE ET AL.
7
thermal decomposition temperatures at 410°C and 260°C and melting
points at 357−359°C and 328−330°C, respectively, indicating that
these two compounds had excellent thermal stability. Meanwhile, both
DACB and BACB could emit strong blue light with quantum yields of
[17] W. Li, A. Zhang, A. D. Schlüter, Chem. Commun. 2008, 43, 5523.
[18] S. Tao, Z. Hong, Z. Peng, W. Ju, X. Zhang, P. Wang, S. Wu, S. Lee,
Chem. Phys. Lett. 2004, 397, 1.
[
[
19] F. Liheng, W. Xiaoju, C. Zhaobin, Anthracene electroluminescence
material containing cavity transmission group and preparation
method: CN101144012A[P]. 2008, 3, 19.
0
.61 and 0.87, respectively. Their electrochemical performance
showed that, through the introduction of the appropriate electron
withdrawing groups and conjugated systems to modify the carbazole
structure, the ability of the electronic transmission of carbazole could
be improved to turn carbazole with typical hole transmission capability
into an ambipolar blue light material. Finally, the electroluminescence
20] K. R. J. Thomas, J. T. Lin, Y.‐T. Tao, C.‐W. Ko, J. Am. Chem. Soc. 2001,
123, 9404.
[21] A. D. Finke, D. E. Gross, A. Han, J. S. Moore, J. Am. Chem. Soc. 2011,
33, 14063.
1
[
[
22] K. Albrecht, K. Yamamoto, J. Am. Chem. Soc. 2009, 131, 2244.
23] P.‐A. Blanche, A. Bablumian, R. Voorakaranam, C. Christenson, W. Lin,
T. Gu, D. Flores, P. Wang, W.‐Y. Hsieh, M. Kathaperumal, B. Rachwal,
O. Siddiqui, J. Thomas, R. A. Norwood, M. Yamamoto, N.
Peyghambarian, Nature 2010, 468, 80.
(
(
EL) device of ITO/NPB (40 nm)/BACB (20 nm)/TPBi (20 nm)/LiF
0.5 nm)/Al (95 nm) with BACB as the emitting layer was fabricated,
and the EL device was shown to emit dark blue light.
[
[
24] H. Aziz, Z. D. Popovic, N.‐X. Hu, A.‐M. Hor, G. Xu, Science 1999, 283,
1
900.
ACKNOWLEDGEMENTS
25] T.‐H. Huang, J. T. Lin, L.‐Y. Chen, Y.‐T. Lin, C.‐C. Wu, Adv. Mater. 2006,
18, 602.
Authors would like to thank Guangzhou City Education System Inno-
vative Academic Team Foundation (Project No. 1201610020) and
key project (Project No. ZSH201609) of Guangzhou Institute of Tech-
nology for financial support.
[26] J. Zaumseil, H. Sirringhaus, Chem. Rev. 2007, 107, 1296.
[27] S. Koichi, S. Akihiro, L. Hiroshi, U. Kazunori, Synth. Met. 2004, 143, 89.
[28] Q. Xiao, R. T. Ranasinghe, A. M. P. Tang, T. Brown, Tetrahedron 2007,
6
3, 3483.
[
[
29] G. Mann, J. F. Hartwig, M. S. Driver, C. Fernández‐Rivas, J. Am. Chem.
Soc. 1998, 120, 827.
ORCID
Shanji Li http://orcid.org/0000-0002-5056-5152
Hui Liang http://orcid.org/0000-0001-7594-5365
30] Y.‐H. Kim, H.‐C. Jeong, S.‐H. Kim, K. Yang, S.‐K. Kwon, Adv. Funct.
Mater. 2005, 15, 1799.
[
[
31] K. Rurack, Springer Ser. Fluoresc. 2008, 5, 101.
REFERENCES
32] T. Zhang, D. Liu, Q. Wang, R. Wang, H. Ren, J. Li, J. Mater. Chem. 2011,
21, 12969.
[
[
1] T. Chenc, C. L. Chiang, Y. C. Lin, Org. Lett. 2003, 5, 126l.
2] N. T. Gurin, K. V. Paksyutov, M. A. Terentev, A. V. Shirokov, Tech. Phys.
[33] S. Janietz, D. D. C. Bradley, M. Grell, C. Giebeler, M. Inbasekaran, E. P.
2012, 57, 308.
Woo, Appl. Phys. Lett. 1998, 73, 2453.
[
3] Z. Gao, Z. Wang, T. Shan, Y. Liu, F. Shen, Y. Pan, H. Zhang, X. He, P. Lu,
B. Yang, Y. Ma, Org. Electron. 2014, 15, 2667.
[34] M.‐Y. Lai, C.‐H. Chen, W.‐S. Huang, J. T. Lin, T.‐H. Ke, L.‐Y. Chen,
M.‐H. Tsai, C.‐C. Wu, Angew. Chem. Int. Ed. 2008, 47, 581.
[
[
[
[
4] D. Y. Kim, H. N. Cho, C. Y. Kim, Prog. Polym. Sci. 2000, 25, 1089.
5] U. Mitschke, P. Le Bauer, J. Mater. Chem. 2000, 10, 1471.
6] J. M. Shi, C. W. Tang, Appl. Phys. Lett. 2002, 80, 3201.
[35] Y.‐L. Liao, C.‐Y. Lin, K.‐T. Wong, T.‐H. Hou, W.‐Y. Hung, Org. Lett.
2
007, 9, 4511.
[
[
[
[
36] C.‐C. Chi, C.‐L. Chiang, S.‐W. Liu, H. Yueh, C.‐T. Chen, C.‐T. Chen,
J. Mater. Chem. 2009, 19, 5561.
7] W.‐J. Shen, R. Dodda, C.‐C. Wu, F.‐I. Wu, T.‐H. Liu, H.‐H. Chen, C. H.
Chen, C.‐F. Shu, Chem. Mater. 2004, 16, 930.
37] S.‐H. Liao, J.‐R. Shiu, S.‐W. Liu, S.‐J. Yeh, Y.‐H. Chen, C.‐T. Chen, T. J.
Chow, C.‐I. Wu, J. Am. Chem. Soc. 2009, 131, 763.
[
8] K.‐T. Wong, Y.‐Y. Chien, R.‐T. Chen, C.‐F. Wang, Y.‐T. Lin, H.‐H.
Chiang, P.‐Y. Hsieh, C.‐C. Wu, C. H. Chou, Y. O. Su, G.‐H. Lee, S.‐M.
Peng, J. Am. Chem. Soc. 2002, 124, 11576.
38] S.‐L. Lin, L.‐H. Chan, R.‐H. Lee, M.‐Y. Yen, W.‐J. Kuo, C.‐T. Chen, R.‐J.
Jeng, Adv. Mater. 2008, 20, 3947.
39] C.‐L. Chiang, M.‐F. Wu, D.‐C. Dai, Y.‐S. Wen, J.‐K. Wang, C.‐T. Chen,
Adv. Funct. Mater. 2005, 15, 231.
[9] A. Saitoh, N. Yamada, M. Yashima, K. Okinaka, A. Senoo, K. Ueno, D.
Tanaka, R. Yashiro, SID Int. Synip. 2004, 35, 150.
[
[
40] C. L. Chiang, C. F. Shu, C. T. Chen, Org. Lett. 2005, 7, 3717.
[10] G.‐L. Feng, W.‐Y. Lai, S.‐J. Ji, W. Huang, Tetrahedron Lett. 2006, 47, 7089.
[11] M. Guan, Z. Q. Bian, Y. F. Zhou, Chem. Commun. 2003, 21, 2708.
[12] S. H. Kim, I. Cho, M. K. Sim, S. Park, S. Y. Park, J. Mater. Chem. 2011,
41] C.‐L. Chiang, S.‐M. Tseng, C.‐T. Chen, C.‐P. Hsu, C.‐F. Shu, Adv. Funct.
Mater. 2008, 18, 248.
21, 9139.
[
[
13] J.‐Y. Shen, X.‐L. Yang, T.‐H. Huang, J. T. Lin, T.‐H. Ke, L.‐Y. Chen, C.‐C.
How to cite this article: Xie P, Yuan N, Li S, Ouyang Y, Zhu Y,
Liang H. Synthesis and properties of blue luminescent bipolar
materials constructed with carbazole and anthracene units with
Wu, M.‐C. P. Yeh, Adv. Funct. Mater. 2007, 17, 983.
14] Y.‐K. Wang, Q. Sun, S.‐F. Wu, Y. Yuan, Q. Li, Z.‐Q. Jiang, M.‐K. Fung,
L.‐S. Liao, Adv. Funct. Mater. 2016, 26, 7929.
4‐cyanophenyl substitute at the 9‐position of the carbazole unit.
[15] M. Pope, H. P. Kallmann, P. Magnante, J. Chem. Phys. 1963, 38, 2042.
Luminescence. 2018;1–7. https://doi.org/10.1002/bio.3452
[16] W. Li, A. Zhang, K. Feldman, P. Walde, A. D. Schlüter, Macromolecules
2008, 41, 3659.