Efficient Nondoped Pure Blue Organic Light-Emitting Diodes Based on an Anthracene and 9,9-Diphenyl-9,10-dihydroacridine Derivative

Article abstract of DOI:10.1002/asia.201901376

Organic light-emitting diodes (OLEDs) have been greatly developed in recent years owing to their abundant advantages for full-color displays and general-purpose lightings. Blue emitters not only provide one of the primary colors of the RGB (red, green and blue) display system to reduce the power consumption of OLEDs, but are able able to generate light of all colors, including blue, green, red, and white by energy transfer processes in devices. However, it remains a challenge to achieve high-performance blue electroluminescence, especially for nondoped devices. In this paper, we report a blue light emitting molecule, DPAC-AnPCN, which consists of 9,9-diphenyl-9,10-dihydroacridine and p-benzonitrile substituted anthracene moieties. The asymmetrically decoration on anthracene with different groups on its 9 and 10 positions combines the merits of the respective constructing units and endows DPAC-AnPCN with pure blue emission, high solid-state efficiency, good thermal stability and appropriate HOMO and LUMO energy levels. Furthermore, DPAC-AnPCN can be applied in a nondoped device to effectively reduce the fabrication complexity and cost. The nondoped device exhibits pure blue electroluminescence (EL) locating at 464 nm with CIE coordinates of (0.15, 0.15). Moreover, it maintains high efficiency at relatively high luminescence. The maximum external quantum efficiency (EQE) reaches 6.04 % and still remains 5.31 % at the luminance of 1000 cd m^?2 showing a very small efficiency roll-off.

Full text of DOI:10.1002/asia.201901376

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Efficient Nondoped Pure Blue Organic Light Emitting Diodes
Based on Anthracene and 9,9-Diphenyl-9,10-dihydroacridine
Derivative
Authors: Ping Lu, Xin He, Shenghong Ren, Hui Liu, Shiyuan Zhao,
Futong Liu, Chunya Du, Jiarui Min, and Haiquan Zhang
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10.1002/asia.201901376
Chemistry - An Asian Journal
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Efficient Nondoped Pure Blue Organic Light Emitting Diodes
Based on Anthracene and 9,9-Diphenyl-9,10-dihydroacridine
Derivative
Xin He+,[a] Shenghong Ren+,[a] Hui Liu,[a] Shiyuan Zhao,[a] Futong Liu,[a] Chunya Du,[a] Jiarui Min, [b]
Haiquan Zhang*,[b] and Ping Lu*,[a]
Dedication ((optional))
Abstract: Organic light emitting diodes (OLEDs) have been full-color displays.[1] Although some OLEDs products in flat-
greatly developed in recent years owing to their abundant panel display fields such as mobile phones and televisions have
advantages for full-color displays and general-purpose lightings. been commercially available in recent years, there still exists
Blue emitters not only provide one of the primary colors of the RGB several bottlenecks for their wide applications. A critical one is
(red, green and blue) display system to reduce the power
the lack of highly efficient blue materials.[2] Blue emission not
consumption of OLEDs, but also are able to generate light of all only represents one of the primary colors of the RGB (red, green
colors, including blue, green, red, and white by energy transfer and blue) display system to effectively reduce the power
processes in devices. However, it remains challenge to achieve
consumption of devices, but also serves as host materials for
other low energy dopants to fabricate RGB/white OLED devices
high-performance blue electroluminescence, especially for
nondoped devices. In this paper, we report a blue light emitting by energy transfer process.[3] In particular, the performance of
molecule, DPAC-AnPCN, which consists of 9,9-diphenyl-9,10- pure blue materials is far from satisfaction in terms of device
dihydroacridine and p-benzonitrile substituted anthracene moieties. efficiency and stability for commercialization as compared with
The asymmetrically decoration on anthracene with different groups their red and green counterparts.[4] Therefore, developing blue
on its
9
and 10 positions combines the merits respective
emitting materials with high efficiency is of significant importance.
Traditional blue fluorescent materials can only provide limited
constructing units and endows DPAC-AnPCN with pure blue
emission, high solid-state efficiency, good thermal stability and EQE because they can only use singlet excitons, which
appropriate HOMO and LUMO energy levels. Furthermore, DPAC- constitutes 25% electrically generated excitons according to the
AnPCN can be applied in nondoped device to effectively reduce the electron spin statistics, to emit fluorescence.[5] In order to break
fabrication complexity and cost. The nondoped device exhibits pure through the predicament, phosphorescent materials based on Ir
blue electroluminescence (EL) locating at 464 nm with CIE or Pt heavy metals are extensively developed which can harvest
coordinates of (0.15, 0.15). It also can keep high efficiency at both singlet and triplet excitons to achieve hundred percent
relatively high luminescence. The maximum external quantum internal quantum efficiency (IQE). But these unsustainable
efficiency (EQE) reaches 6.04% and still remains 5.31% at the
luminance of 1000 cd m-2 showing a very small efficiency roll-off.
phosphorescent complexes are rather expensive and noxious
which also hampers their long-term application.[6] Thermally
activated delayed fluorescence (TADF) is another effective way
to attain 100% IQE though reverse intersystem crossing (RISC)
process from lowest triplet excited state (T1) to the lowest singlet
excited state (S1).[7] However, OLEDs based on these two kinds
of materials often needs to be doped into proper host materials
with appropriate doping concentration to get ideal device
performances.The doping strategy will complicate the device
fabrication procedures and increase the device cost.[8] In
addition, they also suffer from varying degrees of efficiency roll-
offs caused by triplet-triplet quenching at high luminescence,
which is an obstacle for their applications.[9] Recently, many
researchers endeavor to develop pure organic blue materials for
nondoped devices.[10] These materials with no TADF property
achieve appreciable device performance with high luminance
and ideal efficiency roll-off. But the EQE of these fluorescent
materials are not comparable and the material structures are
limited to several aromatic fused rings, which hinder the
development of nondoped blue devices. Therefore, the
developing of pure organic blue materials with high efficiency
and novel molecular structure which is designed for nondoped
Introduction
Organic light emitting diodes (OLEDs) have progressed rapidly
since its first discovery by C. W. Tang and VanSlyke in 1987 for
their promising applications as solid-state lighting sources and
[a]
Dr. X. He, Dr. S. Ren, Dr. H. Liu, Dr. S. Zhao, Dr. F. Liu, Dr. C. Du,
Prof. P. Lu
Department of Chemistry
Jilin University
State Key Laboratory of Supramolecular Structure and Materials
2699 Qianjin Avenue, Changchun 130012 (P. R. China)
E-mail: lup@jlu.edu.cn
[b]
Dr. J. Min, Prof. H. Zhang
Yanshan University
State Key Laboratory of Metastable Materials Science and
Technology
E-mail: hqzhang@ysu.edu.cn
[+]
These authors contributed equally to this work.
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device retains great significance for both science research and
practical applications.
and then get boronated to obtain the precursor DPACB. dBrAn
was substituted on one side with benzyl cyanide group via
Suzuki coupling reaction to get AnPBrCN. Finally, DPACB was
coupled with AnPBrCN to attain target molecule DPAC-AnPCN.
The crude product was purified by column chromatography, and
then elaborate characterization including mass spectrum (MS),
NMR measurement and elemental analysis (EA) were
performed to confirm the structure of DPAC-AnPCN. The details
of the characterization data are summarized in the Supporting
Information (SI).
In this work, DPAC-AnPCN is reported as a highly efficient
blue-emitting material which is constructed by connecting 9,9-
diphenyl-9,10-dihydroacridine (DPAC)
with p-benzonitrile
substituted anthracene. Anthracene is an efficient chromophore
of blue fluorescence with high photoluminescence quantum yield
(PLQY) owing to its rigid planar structure.[11] Besides, anthracene
has two reaction sites on its 9 and 10 positions,so that
asymmetrically decoration on anthracene with different groups
can be realized. Further, anthracene possesses appropriate
wide bandgap which ensures the blue emission of its
derivatives.[12] DPAC is introduced as a weak electron donor
group which is connected with anthracene through a bridging
benzene. DPAC has higher highest occupied molecular orbital
(HOMO) than anthracene to effectively reduce hole injection
barrier in its devices.[13] On the other site of anthracene, p-
benzonitrile group is introduced as electron-withdrawing group
which can lower the LUMO energy level of target molecule to
reduce electron injection barrier and modify the emission
wavelength. As a result, 4-(10-(4-(9,9-diphenylacridin-10(9H)-
Thermal properties
Thermal properties of DPAC-AnPCN were examined by
thermal gravimetric analysis (TGA) and differential scanning
calorimetry (DSC). As shown in Figure 1a, The decom-
position temperature (Td, corresponding to 5% weight loss)
of DPAC-AnPCN was 426 °C, indicating that DPAC-AnPCN
could endure high temperature and would not go through
decomposition during device fabrication and operation. The
DSC data of the target molecular was shown in Figure 1b.
Upon heating procedure, no obvious exo- or endothermic
signal could be seen until the melting point (Tm) occurs at
342 °C. No glass transition temperature (Tg) could be
observed in the scan range from 50 oC to 375 oC,
demonstrating that DPAC-AnPCN would keep stable
morphology which is significant and essential for OLEDs
applications.
yl)phenyl)anthracen-9-yl)benzonitrile
(DPAC-AnPCN)
is
successfully achieved which exhibits blue emission with high
PLQY of 65% in its pure film. Especially, the non-doped OLED
using DPAC-AnPCN as the active layer shows the maximum
EQE of 6.04% with EL peak of 464 nm and a very low efficiency
roll-off. The CIE coordinates locate at (0.15, 0.15), which
matches well with the criteria of pure blue OLEDs.
(a)
(b)
5% weight loss
100
80
60
40
20
0
first heating
first cooling
Results and Discussion
Synthetic procedures
DPAC-AnPCN
Td = 426 o
C
second heating
0
200
400
600
50
100
150
200
250
300
350
Temperature (oC)
Temperature (oC)
Figure 1. TGA (a) and DSC (b) graphs of DPAC-AnPCN. Heating rate:
10 °C·min-1.
(b)
1% doped in
PMMA
(a)
Abs in THF
PL in THF
neat film
Scheme 1. Synthesis route of DPAC-AnPCN. a) Ullmann coupling reaction:
CuI, trans-1,2-cyclohexanediamine (DACH), tert-butoxide, toluene, 110 ℃, 18
h; b) Miyaura boronization reaction: Pd(dppf)Cl2, KOAc, 1,4-dioxane, 85 ℃; c)
Suzuki coupling reaction: Pd(PPh3)4, K2CO3, toluene, 90℃, 12h to afford
AnPBrCN and 24 h to afford DPAC-AnPCN. All the reactions mentioned above
are protected by nitrogen atmosphere.
400
450
500
550
600
300
400
500
600
700
Wavelength (nm)
Wavelength (nm)
Figure 2. (a) The UV-vis and PL spectra of DPAC-AnPCN in dilute THF
solution with concentration of 10-5 M; (b) PL spectra of DPAC-AnPCN in
films.
The synthetic route to DPAC-AnPCN was shown in Scheme 1.
DPAC was decorated on the N-site with bromobenzene group
Photophysical properties
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The UV/Vis absorption and photoluminescence (PL)
spectra of DPAC-AnPCN were recorded in various solvents
with different polarities with a dilute concentration of 10-5 M.
As shown in Figure 2a, the molecule showed sharp
absorption peaks at 357 nm, 375 nm and 395 nm in THF,
which was attributed to characteristic absorption of
anthracene group. Another unstructured trailing absorption
peak around 406 nm could be identified to the CT
absorption of the molecule. Obvious solvatochromic
phenomenon was observed of DPAC-AnPCN in the
measurement of emission spectra in different solvents
which is shown in 3a. The emission peak of DPAC-AnPCN
shifted 100 nm from 438 nm in low-polar solvent n-hexane
to 538 nm in high-polar solvent acetonitrile, indicating the
strong CT property of the S1 state. This CT property was
well matched the calculation results. The energy level of S1
of DPAC-AnPCN was calculated to be 2.77 eV, which came
from the emission peak of toluene (447 nm). Then DPAC-
AnPCN was dispersed into polymethyl mechacrylate
(PMMA) with concentration of 1 wt%. The prepared DPAC-
AnPCN PMMA doped film showed emission peak at 449
nm and the pure thin film shows at 454 nm. (Figure 2b)
The transient PL decay of the molecule was further
measured and showed in Figure 3b. The molecular show
one-exponential PL decays in THF with lifetime of 9.38 ns,
and 5.62 ns for its PMMA doped film (Figure S7). No
delayed component could be detected, indicating that the
emission of the molecule in both states absolutely
originated from the directly decay of S1 state. The PLQYs of
the DPAC-AnPCN nondoped and doped films were similar,
which are measured to be 65% and 61% using integrating
sphere, respectively, indicating that the solid DPAC-AnPCN
maintain high radiative transition rate after aggreagating.
Theoretical calculations and electrochemical properties
Theoretical calculations were performed to forecast the
properties of DPAC-AnPCN. The optimized configuration of the
molecule showed distinctive structure of DPAC moiety, which
had a spatial vertical benzene group at the 10 site of acridine.
This might make DPAC-AnPCN bigger volume and weaken the
intermolecular interactions. This was similar to our former work
on DPAC based crystal.[13-a] Then, the HOMO and LUMO
distributions of DPAC-AnPCN were calculated by the method of
density functional theory (DFT). As shown in Figure S10, the
HOMO of the molecule was mostly distributed on the DPAC
moiety while the LUMO was mainly distributed on the
anthracene and p-benzonitrile moieties. The overlap of HOMO
and LUMO was small which indicated the strong intramolecular
charge transfer characteristic of DPAC-AnPCN. Then natural
transition orbitals (NTO) of the singlet and triplet states were
calculated with TD-DFT method to predict the excited states
properties of the molecule (Figure S11). The S1 of DPAC-
AnPCN showed obvious charge transfer property. This might
mainly owe to the electron-withdrawing ability of the p-
benzonitrile group, which lowered the CT energy of DPAC-
AnPCN. The calculated T1 of DPAC-AnPCN was localized state
concentrating on anthracene group, which was similar to other
reported An-based molecules. The energy levels of S1 and T1 of
DPAC-AnPCN were calculated to be 3.50 eV and 2.13 eV,
respectively, which fitted 2T1＞S1 providing possibility of triplet-
triplet annihilation of anthracene group.
Similar
emission
wavelength
implied
that
little
intermolecular interactions worked in the nondoped
condition. Both films showed unstructured board emission
peak which coordinates with the states in the solvents.
Similar with the former work based on anthracene, the
phosphorescence of DPAC-AnPCN could hardly be gained
with the method tested using spectrometer in frozen 2-
methy THF at 77K. The main reason was that the low-
positioned T1 of An group made a narrow band gap
between T1 and S0. According to the energy gap law, the
dominating way of consuming T1 energy might be
nonradiative transition but not the decay from T1 to S0. Thus,
PtOEP was introduced as a triplet sensitizer followed the
reported method.[14] The first vibrational peak of
phosphorescence of the molecule was 713 nm, then the T1
energy level was calculated to be 1.74 eV. (Figure S6) So
the phosphorescence originated from the An group, which
was the same as other researches of An.
The HOMO/LUMO energy levels of DPAC-AnPCN were
estimated from cyclic voltammetry (Figure 4). The oxidation
potential is originated mainly from electron donor DPAC, while
the reduction potential is determined by benzonitrile-substituted
anthracene. The oxidation and reduction onset against
ferrocenium/ferrocene (Fc+/Fc) redox couple of DPAC-AnPCN
were 0.74 V and -1.74 V, respectively, referring to the calculated
HOMO and LUMO energy levels of −5.54 eV and −3.06 eV. The
HOMO/LUMO calculation was essential for adjustment of the
device structures to achieve suitable energy levels between
emitting and transporting materials which could avoid interface
emitting and other problems in devices. This is also propitious to
improve the device performance.
105
(a)
(b)
DPAC-AnPCN
IRF
HEX
TOL
ETE
THF
ACN
104
103
102
101
in THF
0
50
100
150
200
400
500
600
700
Time (ns)
Wavelength (nm)
Figure 3. (a) Solvatochromic PL spectra of DPAC-AnPCN with
increasing polarity of solvents; (b) Transient PL decay of DPAC-AnPCN
in dilute THF (Concentration: 10-5 M).
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cyclohexan) is the hole transporting layer (HTL), TCTA
(tris(4-carbazoyl-9-ylphenyl)amine) is the buffer layer,
DPAC-AnPCN is the emitting layer (EML), TPBi (1,3,5-tris-
(N-phenylbenzimidazol-2-yl)benzene) is the electron
transporting layer, LiF is the electron injecting layer and Al
is the cathode. The DPAC-AnPCN nondoped device
(Device A) showed stable EL emission under various
driving voltages and peaked at 464 nm with CIE
coordinates of (0.15, 0.15) at 4 V, which accorded with the
PL spectra from the nondoped thin films (Figure 5). Device
A was turned on at a low voltage of 3 V, which proved that
the carrier injection and recombination worked efficiently in
the device. The maximum EQE of device A was 6.04%,
which is among the best results nondoped fluorescent blue
OLEDs. The EQE of device A remained 5.31% at a high
luminescence of 1000 cd m-2 (Table S2) with a small
efficiency roll-off, which fitted the original intention of
introducing DPAC group. Further, we also fabricated doped
device for DPAC-AnPCN (device B) and adjusted the
device structure. After optimizing the thickness of the carrier
transporting layers and changing the host materials with
modified doping concentration, the best result of device B
was gained with the structure of ITO/HATCN (6 nm)/TAPC
(25 nm)/TCTA (15 nm)/CBP:DPAC-AnPCN-30% (20
nm)/TPBI (40 nm)/LiF(1 nm)/Al, where 4,4-di(9H-carbazol-
9-yl)-1,1-biphenyl (CBP) was the chosen host material for
DPAC-AnPCN, and the doping concentration was optimized
to be 30% to reach the best performance. The doped
device also shows stable deep blue emission peak at 452
nm with CIE coordinates of (0.15, 0.09). Device B achieved
a maximum EQE of 5.99% and remains 3.32% at 1000 cd
m-2 (Figure S9, Table S2). Nearly half of the EQE rolled at
high luminescence, which was mainly because that the
accumulated excitons were quenched or consumed rather
than emit. In consideration of the efficiency roll-off
behaviors of the nondoped and doped devices of DPAC-
AnPCN, TTA might happen to explain the phenomenon.
The TTA process might be effective at low voltage which
contributed to the similar maximum EQE of both devices.
But at high voltage of luminescence, DPAC-AnPCN in
nondoped device gained much more opportunities to
collision than the doped device, resulting in more additional
emissive S1 exitons from TTA process.
E
= 0.74 V
ox
E
= -1.74 V
-1.0
red
-2.0
-1.5
0.5
1.0
+
Potential V vs. Fc/Fc
Figure 4. Cyclic voltammograms scans of DPAC-AnPCN, the potentials
are calibrated against Fc+/Fc internal standard.
Device A
500
400
300
200
100
0
Device A
(a)
4 V
5 V
6 V
7 V
8 V
9 V
10 V
11 V
103
102
101
100
(b)
400
500
600
700
3
4
5
6
7
8
9
10 11
Wavelength (nm)
Voltage (V)
102
(c)
Device A
101
100
10-1
100
101
102
103
104
Luminance (cd m-2)
Figure 5. (a) EL spectra of Device A at different driving voltages; (b)
Luminance-Voltage-Current Density curves of device A; (c) Luminance-
EQE curve of device A.
Table 1. EL data of device based on DPAC-AnPCN.
[b]
[c]
[e]
V[a]
(V)
Lmax
CEmax
EQE[d]
(%)
λEL
CIE[f]
(x,y)
Device
A
(cd·m-2)
(cd·A-1)
(nm)
3.0
7929
7.26
6.04
464
(0.15, 0.15)
[a] Turn-on voltage at a luminance of 1 cd·m-2; [b] Maximum brightness;
[c] Maximum current efficiency; [d] Maximum external quantum efficiency;
[e] EL emission peak at 4V; [f] CIE coordinates at 4V.
Electroluminescent properties
Conclusions
To investigate the electroluminescent (EL) performance of
DPAC-AnPCN, we fabricated the nondoped OLEDs devices
with structure of indium tin oxide (ITO)/HATCN (6
nm)/TAPC (20 nm)/TCTA (20 nm)/DPAC-AnPCN (20
nm)/TPBi (40 nm)/LiF(1 nm)/Al, where ITO is the anode,
hexaazatriphenylenehexacarbonitrile (HATCN) is the hole
injecting layer (HIL), TAPC (di-(4-(N,N-ditolyl-amino)-phenyl)
In summary, an efficient blue emitter DPAC-AnPCN using DPAC
as the donor, substituted anthracene as respective acceptor is
synthesized. The PLQYs of the DPAC-AnPCN nondoped and
doped films were similar, which are measured to be 65% and
61%. The doped device shows a stable deep blue emission
peaking at 452 nm with CIE coordinates of (0.15, 0.09). The
maximum EQE is 5.99% and remains 3.32% at 1000 cd m-2. The
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nondoped device based on DPAC-AnPCN shows a maximum
EQE of 6.04% with the CIE coordinates of (0.15, 0.15). The
efficiency roll-off of DPAC-AnPCN nondoped device is rather
small at the luminance of 1000 cd m-2 remaining an EQE of
5.31%. The introduction of DPAC moiety weakens the
intermolecular interactions and restrains the aggregation
quenching effect. This provides promising molecule design
strategies of materials for nondoped blue OLED devices. This
result is among the best of nondoped blue fluorescent OLEDs.
We believe that our work is valuable for further scientific
researches and practical applications such as lightings and
display technologies.
40 mmol), 20 mL distilled water, 40 mL toluene and Pd(PPh3)4 (230 mg,
0.20 mmol) was added and refluxed at 90 °C under nitrogen atmosphere
for 18 hours. The mixture was poured into water to quench the reaction
and then extracted with DCM, the organic layer was collected and
combined. After evaporation of the solvent, the residue was purified by
column chromatography by using petroleum ether/DCM (4:1, v/v) as
eluent to afford greenish solid. (1.97 g, yield: 55%). 1H NMR (500 MHz,
DMSO-D6, 25 °C, TMS) δ (ppm): 8.66 (d, J = 8.9 Hz, 2H; Ar H), 7.92 (m,
2H; Ar H), 7.64 (ddd, J = 8.9 Hz, 6.4 Hz, 1.1 Hz, 2H; Ar H), 7.56 (m, 2H;
Ar H), 7.52 (d, J = 8.7 Hz, 2H; Ar H), 7.44 (m, 2H; Ar H). MALDI-TOF MS
(mass m/z): calcd for C21H12BrN, 357.02; found, 358.01 [M+].
Synthesis of DPAC-AnPCN
In a 100 mL round flask, a mixture of AnPBrCN (1.32 g, 4 mmol), DPACB
(2.14 g, 4 mmol), K2CO3 (5.52 g, 40 mmol), 20 mL distilled water, 40 mL
toluene and Pd(PPh3)4 (230 mg, 0.2 mmol) was added and refluxed at
90 °C under nitrogen atmosphere for 24 hours. The mixture was poured
into water to quench the reaction and then extracted with DCM, the
organic layer was collected and combined. After evaporation of the
solvent, the residue was purified by column chromatography by using
petroleum ether/DCM (1:1, v/v) as eluent to afford white solid. (2.47 g,
yield: 90%). 1H NMR (500 MHz, DMSO-D6, 25 °C, TMS) δ (ppm): 8.16 (d,
J = 8.0 Hz, 2H; Ar H), 7.75 (d, J = 7.7 Hz, 4H; Ar H), 7.71 (d, J = 7.8 Hz,
2H; Ar H), 7.54 (dd, 6H; Ar H), 7.20-7.39 (m, 10H; Ar H), 6.92-7.06 (m,
6H; Ar H), 6.85 (d, J = 8.0 Hz 2H; Ar H), 6.71 (d, J = 8.4 Hz, 2H); 13C
NMR (125 MHz CDCl3, 25 oC, TMS): δ= 146.37, 144.32, 144.23, 142.27,
140.21, 138.67, 137.13, 134.95, 133.40, 132.32, 131.44, 130.45, 130.09,
129.74, 129.44, 127.68, 126.99, 126.26, 125.85, 125.55, 120.39, 118.55,
114.15, 111.50 (ppm). MALDI-TOF MS (mass m/z): calcd for C52H34N2,
686.27; found, 686.9 [M+]. Anal. Calcd (%) for C52H34N2: C, 90.93; H,
4.99; N, 4.08. Found: C, 90.81; H, 5.03; N, 4.16.
Experimental Section
General information
All the reagents and solvents used for the syntheses were
purchased from Aldrich and Acros and used as received.
Synthetic procedures
Synthesis of DPACBr
In a 250 mL round flask, a mixture of DPAC (6.67 g, 20 mmol), 1-bromo-
4-iodobenzene (8.49 g, 30 mmol), copper(I) iodide (190 mg, 1 mmol),
DACH (1.20 ml, 10 mmol), sodium tert-butoxide (2.88 g, 30 mmol) and
100 ml toluene were stirred and refluxed at 110 °C for 12 hours under
nitrogen protection. Then the mixture was cooled to room temperature
and poured into 100 mL water and extract with dichloromethane (DCM).
Then the organic layer was separated and combined. After evaporating
the solvent, the residue was further purified by column chromatography
with petroleum ether/DCM (4:1, v/v) as the eluent. Finally, the crude
product was recrystallized from ethanol to afford white solid. (6.93 g, yield:
71%). 1H NMR (500 MHz, DMSO-D6, 25 °C, TMS) δ (ppm): 7.83 (d, J =
8.5 Hz, 2H), 7.33 (t, J = 7.3 Hz, 4H), 7.28 (t, J = 7.1 Hz, 2H), 7.10 (t, J =
7.1 Hz, 2H), 7.03 (d, J = 8.5 Hz, 2H), 6.93 (d, J = 7.6 Hz, 2H), 6.90 (d, J =
7.5 Hz, 4H), 6.78 (d, J = 7.7 Hz, 2H), 6.35 (d, J = 8.1 Hz, 2H); MALDI-
TOF MS (mass m/z): calcd for C31H22BrN, 487.09; found, 487.61 [M+].
Synthesis of DPACB
Acknowledgements
This research is supported by the National Basic Research
Program of China (Grant No. 2016YFB0401001), National
Natural Science Foundation of China (91833304,21774047) and
the Jilin Provincial Science and Technology Department
(20180201084GX) and the Fundamental Research Funds for
the Central Universities.
In a 250 mL round flask, a mixture of DPACBr (5.86 g, 12 mmol),
bis(pinacolato)diboron
(6.10
g,
24
mmol),
1,1’-
bis[(diphenylphosphino)ferrocene]dichloropalladium PdCl2(dppf)2 (288
mg, 0.36 mmol), potassium acetate (3.54 g, 36 mmol) and 100 ml
dioxane were stirred and refluxed at 85 °C for 24 hours under nitrogen
protection. The reaction mixture was extracted with DCM and further
purified by column chromatography using petroleum ether/DCM (2:1 v/v)
as eluent to attain product as white solid. (2.57g, yield: 40%). 1H NMR
(500 MHz, DMSO-D6, 25 °C, TMS) δ (ppm): 7.92 (d, J = 6.5 Hz, 2H),
7.31 (dt, J = 20.6, 5.7 Hz, 6H), 7.11 (d, J = 6.4 Hz, 2H), 7.07 (t, J = 6.4
Hz, 2H), 6.91 (t, J = 6.4 Hz, 6H), 6.78 (d, J = 6.2 Hz, 2H), 6.31 (d, J = 6.6
Hz, 2H), 1.34 (s, 12H); MALDI-TOF MS (mass m/z): calcd for
C31H34BNO2, 535.27; found, 535.91 [M+].
Keywords: anthracene • blue emission • high solid-state
efficiency • low efficiency roll-off • OLED
[1]
[2]
C. W. Tang, S. A. VanSlyke, Appl. Phys. Lett. 1987, 51, 913.
(a) M. Zhu, C. Yang, Chem. Soc. Rev. 2013, 42, 4963; (b) X. Zhan, Z.
Wu, Y. Lin, Y. Xie, Q. Peng, Q. Li, D. Ma, Z. Li, Chem. Sci. 2016, 7,
4355; (c) B. Chen, B.Liu, J. Zeng, H. Nie, Y. Xiong, J. Zou, H. Ning, Z.
Wang, Z. Zhao, B. Z. Tang, Adv. Funct. Mater. 2018, 28, 1803369.
(a) S. Reineke, F. Lindner, G. Schwartz, N. Seidler, K. Walzer, B.
Luessem, K. Leo, Nature 2009, 459, 234; (b) X. Sun, J. Li, H. Liu, P. Lu,
Actc Polym. Sin. 2018, 2, 284; (c) D. Zhang, L. Duan, Y. Zhang, M. Cai,
D. Zhang, Y. Qiu, Light: Sci. Appl. 2015, 4, e232.
[3]
Synthesis of AnPBrCN
In a 100 mL round flask, a mixture of 9,10-dibromoanthracene (3.36 g, 10
mmol), (4-cyanophenyl)boronic acid (1.48 g, 10 mmol), K2CO3 (5.52 g,
For internal use, please do not delete. Submitted_Manuscript
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[4]
(a) X. Sun, L. Zhao, X. Han, H. Liu, Y. Gao, Y. Tao, H. Zhang, B. Yang,
P. Lu, Molecules 2018, 23, 190; (b) Y. Xu, X. Liang; X. Zhou, P. Yuan, J.
Zhou, C. Wang. B. Li, D. Hu, X. Qiao, X. Jiang, L. Liu, S. J. Su, D. Ma,
Y. Ma, Adv. Mater. 2019, 31, 1807388.
Z. Wu, G. Xie, C. Zhong, Z. Zhu, H. Cong, D. Ma, C. Yang, Chem.
Commun. 2016, 52, 11012.
[10] (a) Y. Li, Z. Xu, X. Zhu, B. Chen, Z. Wang, B. Xiao, J. W. Y. Lam, Z.
Zhao, D. Ma, B. Z. Tang, ACS Appl. Mater. Interfaces 2019, 11, 17592;
(b) Z. Li, C. Li, Y. Xu, N. Xie, X. Jiao, Y. Wang, J. Phys. Chem. Lett.
2019, 10, 842; (c) Y. Yuan, J.-X. Chen, F. Lu, Q.-X. Tong, Q.-D. Yang,
H.-W. Mo, T.-W. Ng, F.L. Wong, Z.-Q. Guo, J. Ye, Z. Chen, X.-H.
Zhang, C.-S. Lee, Chem. Mater. 2013, 25, 4957.
[5]
(a) M. A. Baldo, D. F. O’Brien, Y. You, A. Shoustikov, S. Sibley, M. E.
Thompson, S. R. Forrest, Nature 1998, 395, 151; (b) M. A. Baldo, D. F.
O’Brien, M. E. Thompson, S.R. Forrest, Phys. Rev. B: Condens. Matter
Mater. Phys. 1999, 60, 14422.
[6] (a) C. Adachi, M. A. Baldo, M. E. Thompson, S. R. Forrest, J. Appl. Phys. [11] (a) R. Kim, S. Lee, K.-H. Kim, Y.-J. Lee, S.-K. Kwon, J.J. Kim, Y.-H. Kim,
2001, 90, 5048; (b) K. S. Yook, J. Y. Lee, Adv. Mater. 2012, 24, 3169;
(c) Y. Tao, C. Yang, J. Qin, Chem. Soc. Rev. 2011, 40, 2943.
(a) H. Uoyama, K. Goushi, K. Shizu, H. Nomura and C. Adachi, Nature,
2012, 492, 234; (b) H. Nakanotani, T. Higuchi, T. Furukawa, K. Masui,
K. Morimoto, M. Numata, H. Tanaka, Y. Sagara, T. Yasuda and C.
Adachi, Nat. Commun., 2014, 5, 4016; (c) S. Hirata, Y. Sakai, K. Masui,
H. Tanaka, S. Y. Lee, H. Nomura, N. Nakamura, M. Yasumatsu, H.
Nakanotani, Q. Zhang, K. Shizu, H. Miyazaki, C. Adachi, Nat. Mater.
2015, 14, 330.
Chem. Commun. 2013, 49, 4664; (b) J.-Y. Hu, Y.-J. Pu, F. Satoh,
S.Kawata, H. Katagiri, H. Sasabe, J. Kido, Adv. Funct. Mater. 2014, 24,
2064.
[7]
[12] (a) J.-Y. Hu, Y.-J. Pu, Y. Yamashita, F. Satoh, S. Kawata, H. Katagiri, H.
Sasabe, J. KIdo, J. Mater. Chem. C, 2013, 1, 3871; (b) H. Liu, L. Kang,
J. Li, F. Liu, X. He, S. Ren, X. Tang, C. Lv, P. Lu, J.Mater. Chem. C,
2019, 7, 10273.
[13] (a) X. He, T. Shan, X. Tang, Y. Gao, J. Li, B. Yang, P. Lu, J.Mater. Chem.
C, 2016, 4, 10205; (b) J. Lee, N. Aizawa, M. Numata, C. Adachi, T.
Yasuda, Adv. Mater. 2017, 29, 1604856; (c) T.-A. Lin, T. Chatterjee,
W.-L. Tsai, W.-K. Lee, M.-J. Wu, M. Jiao, K.-C. Pan, C.-L. Yi, C.-L.
Chung, K.-T. Wong, Adv. Mater. 2016, 28, 6976.
[8]
[9]
(a) X. Tang, Y. Tao, H. Liu, F. Liu, X. He, Q. Peng, J. Li, P. Lu,
Luminescence. Front. Chem. 2019, 7, 373 (b) Q . Zhang, J. Li, K. Shizu,
S. Huang, S. Hirata, H. Miyazaki, C. Adachi, J. Am. Chem. Soc. 2012,
134,14706.
[14] (a) L. Yao, Y. Pan, X. Tang, Q. Bai, F. Shen, F. Li, P. Lu, B. Yang, Y.
Ma, J. Phys. Chem. C 2015, 119, 17800; (b) M. Aydemir, G. Haykır, A.
Battal, V. Jankus, S. K. Sugunan, F. B. Dias, H. A. Attar, F. Türksoy, M.
Tavaslı, A. P. Monkman, Org. Electron. 2016, 30, 149.
(a) T.-A. Lin, T. Chatterjee, W.-L. Tsai, W.-K. Lee, M.-J. Wu, M. Jiao, K.-
C. Pan, C.-L. Yi, C.-L. Chung, K.-T. Wong, C.-C. Wu, Adv. Mater. 2016,
28, 6976; (b) D. R. Lee, B. S. Kim, C. W. Lee, Y. Im, K. S. Yook, S.-H.
Hwang, J. Y. Lee, ACS Appl. Mater. Interfaces 2015, 7, 9625; (c) L. Yu,
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Entry for the Table of Contents
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D-A-A’ type molecule DPAC-AnPCN
shows high PLQY of 65% in its pure
film and strong charge transfer
properties. The nondoped device with
DPAC-AnPCN as emitter achieves a
maximum EQE of 6.04% with small
efficiency roll-off, which EL peaks at
464 nm with CIE coordinates of (0.15,
0.15).This meets well with the criteria
of pure blue OLEDs.
X. He, S. Ren, H. Liu, S. Zhao, F. Liu, C.
Du, J. Min, P. Lu*
Page No. – Page No.
Efficient Nondoped Pure Blue Organic
Light-emitting
Anthracene
Diodes
and 9,9-diphenyl-9,10-
Based
on
dihydroacridine Derivative
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