Synthesis, Characterization and Luminescent Properties of Anthracen- or Pyrene-Based Coumarin Derivatives

Article abstract of DOI:10.1007/s10895-018-2277-5

Three anthracen- or pyrene-based coumarin derivatives have been successfully synthesized and characterized by EA, IR and ¹H NMR. The photophysical properties of all derivatives were investigated by UV-Vis and photoluminescence spectroscopic analysis. Their thermal stabilities were demonstrated by TGA. These compounds exhibit strong blue mission under ultraviolet light excitation and have potential possible to explore organic electroluminescent materials. The vacuum-processed doped devices with a configuration of ITO/TAPC (20?nm)/TBADN: b1 (x wt%, 30?nm)/TPBi (50?nm)/Liq (2?nm)/Al (150?nm) was fabricated, in which the devices based on b1 exhibited the best electroluminescence performance with a maximum brightness of 8165?cd/m² and a maximum luminous efficiencies of 6.13?cd/A and a maximum external quantum efficiency (EQE) of 2.75%.

Full text of DOI:10.1007/s10895-018-2277-5

Journal of Fluorescence
https://doi.org/10.1007/s10895-018-2277-5
ORIGINAL ARTICLE
Synthesis, Characterization and Luminescent Properties of Anthracen-
or Pyrene-Based Coumarin Derivatives
1
1
1
2
1
Hui Zhang & Li Zhao & Qinglong Luo & Yuling Zhao & Tianzhi Yu
Received: 10 April 2018 /Accepted: 7 August 2018
#
Springer Science+Business Media, LLC, part of Springer Nature 2018
Abstract
1
Three anthracen- or pyrene-based coumarin derivatives have been successfully synthesized and characterized by EA, IR and H
NMR. The photophysical properties of all derivatives were investigated by UV-Vis and photoluminescence spectroscopic
analysis. Their thermal stabilities were demonstrated by TGA. These compounds exhibit strong blue mission under ultraviolet
light excitation and have potential possible to explore organic electroluminescent materials. The vacuum-processed doped
devices with a configuration of ITO/TAPC (20 nm)/TBADN: b1 (x wt%, 30 nm)/TPBi (50 nm)/Liq (2 nm)/Al (150 nm) was
fabricated, in which the devices based on b1 exhibited the best electroluminescence performance with a maximum brightness of
2
8
165 cd/m and a maximum luminous efficiencies of 6.13 cd/A and a maximum external quantum efficiency (EQE) of 2.75%.
.
.
.
Keywords Coumarin Anthracen Pyrene Luminescence
Introduction
solar cells, organic field effect transistors (FETs), and fluores-
cent probes [12–14].
Coumarin derivatives were used extensively as potential fluo-
rescence materials and emissive dopants in organic light-
emitting diodes (OLEDs) application due to their favorable
photophysical properties such as large Stokes shifts, high fluo-
rescence quantum yields, excellent light stabilities [1–4].
Anthracene and pyrene are members of the polycyclic ar-
omatic hydrocarbon (PAH) family. They exhibit good planar-
ities enlarged π-conjugation systems [5], strong visible π-π*
absorptions, intense blue fluorescences with high quantum
yields [6], high charge mobilities in the solid state [7, 8], good
thermal stabilities [9] and long fluorescence lifetime [10, 11].
Due to these excellent optical properties, anthracene and
pyrene are used as blue light-emitting materials in OLEDs,
Herein, to achieve novel fluorescent materials with good
properties for OLED application, anthracen- or pyrene-based
coumarin derivatives have been developed, which combine
one or two 7-diethylamino-coumarin arms and an anthracen/
pyrene core.
The synthetic routes and chemical structures of three ma-
terials are shown in Scheme 1.
Experimental
Materials and Instruments
Anthracene were purchased from Shanghai Chemical Reagent
CO. Ltd. 1-Bromopyrene and bis(pinacolato)diboron were an-
alytical grade reagents from Energy Chemical China
Electronic supplementary material The online version of this article
(https://doi.org/10.1007/s10895-018-2277-5) contains supplementary
material, which is available to authorized users.
(Shanghai) Co. Ltd. 1,6-bibromopyrene was analytical grade
reagents from Beijing HWRK Chem Co., LTD. Other re-
agents and solvents were commercially available and were
of AR grade.
*
Tianzhi Yu
yutianzhi@hotmail.com
1
IR spectra were measured on a Shimadzu IR Prestige-21
FT-IR spectrophotometer. C, H, and N analyses were obtained
using an Elemental Vario-EL automatic elemental analysis
instrument. H NMR spectra were obtained on Varian
Mercury Plus 400 MHz and Agilent Technologies DDZ
Key Laboratory of Opto-Electronic Technology and Intelligent
Control (Ministry of Education), Lanzhou Jiaotong University, 88
West Anning Road, Lanzhou 730070, China
1
2
School of Chemical and Biological Engineering, Lanzhou Jiaotong
University, Lanzhou 730070, China

J Fluoresc
Scheme 1 Synthetic routes for 1-
4-(7-N,N′-
diethylaminocoumarin-3-
[
O
O
O
O
Pd (dppf)Cl
1,4-dioxane
2
B
B
O B
O
o
80
C
Br
a1
yl)phenyl]pyrene(b1), 1,6-bis[4-
TBAB
PPh
Na CO
(
3
7-N,N′-diethylaminocoumarin-
-yl)phenyl]pyrene(b2) and 9,10-
(
3
)
4
Pd(0)
N
Br
2
3
O
bis[4-(7-N,N-′
diethylaminocoumarin −3-
yl)phenyl]anthracene(b3)
O
toluene
reflux
a2
N
O
O
b1
Route 1
N
O
O
O
O
Br
B
B
N
O
B
O
O
O
O
O
Br
a3
Br
TBAB
TBAB
(PPh Pd(0)
(
PPh
3
)
4
Pd(0)
3 4
)
Br
Na
2
CO
3
Br
Na CO
2
3
O
O
N
N
N
N
O
O
O
O
O
O
b2
b3
Route 2
6
00 MHz Spectrometer with tetramethylsilane as the internal
H). Anal. Calcd. for C H BO C 80.51, H 6.45. Found: C
22 21 2:
standard. UV-vis absorption and fluorescence spectra were
recorded on a UV-2550 spectrometer and Perkin-Elmer LS-
80.53, H 6.44.
5
5 spectrometer, respectively. MS was obtained from a
Thermo Scientific Orbitrap Elite mass spectrometer. Cyclic
voltammetry (CV) was carried out on an CH Instruments
Preparation of 1-[4-(7-N,N
′-Diethylaminocoumarin-3-Yl)Phenyl]Pyrene (b1)
7
60 B with a three electrode system (a Pt working electrode,
a Pt-wire counter electrode, and a Ag/AgCl reference elec-
3-(4-Bromophenyl)-7-(N,N′-diethylamino)coumarin (a2)
was prepared by the procedure as previously described
[15].
−
1
trode) in the presence of n-Bu NPF (0.1 mol∙L ) as a
4
6
supporting electrolyte in CH Cl . Fluorescent lifetime and
2
2
quantum yield were recorded on a FLSP920 type steady-
state / transient fluorescence spectrometer (Edinburgh
Instruments Ltd).
Compound a1(1 g, 3.05 mmol), compound a2 (1.48 g,
3.965 mmol), TBAB (0.05 g, 0.16 mmol) and (PPh ) Pd(0)
3
4
(0.17 g, 0.15 mmol) were dissolved in the mixture of 20 mL
toluene and 5 mL 2 M Na CO solution. Under nitrogen, the
2
3
resulting mixture was refluxed with stirring for 24 h, and then
the mixture was extracted with CH Cl (3 × 50 mL). The or-
Preparation of 4,4,5,5-Tetramethyl-[1,3,2]
2
2
-
Dioxaborolan-2-Yl-Pyrene(a1)
ganic extracts were combined, dried over anhydrous MgSO4
and concentrated in vacuo. The residue was chromatographed
on silica, eluting with EtOAc/ether/CH Cl (1:15:2–1:15:1
To a solution of bis(pinacolato)diboron (2.71 g, 10.67 mmol),
2
2
Pd(dppf)Cl (0.26 g, 0.36 mmol) and potassium acetate (2.1 g,
gradient) to give the b1 as yellow powder solid (yield 73%).
2
−1
2
1.34 mmol) in absolute 1,4-dioxane (60 mL) was added 1-
m.p.: 258–260 °C. IR (KBr pellet, cm ): 1711(ν
(ν C=C), 1508 (ν Ar C=C), 1131 (ν C-O-C), 848 (ν Ar C-H). H
), 1595
C=O
1
bromopyrene (2 g, 7.11 mmol). The mixture was stirred under
nitrogen at 80 °C for 35 h. To the residue was added saturated
sodium chloride solution and the mixture was extracted with
CH Cl (3 × 50 mL). The combined organic extracts were
NMR (500 MHz, CDCl , δ, ppm): 1.23 (t, J = 7.1 Hz, 6H,
3
CH ), 3.43 (q, J = 7.1 Hz, 4H, CH ), 7.69 (d, J = 8.1 Hz,
3
2
2H), 7.25 (s, 1H), 7.35 (d, J = 8.7 Hz, 1H), 7.68 (s, 2H),
7.84 (s, 1H), 7.91 (d, J = 8.1 Hz, 2H), 8.01 (t, J = 12.6 Hz,
2H), 8.09 (s, 2H), 8.18 (dd, J = 15.7, 7.5 Hz, 2H), 8.22 (d, J =
7.8 Hz, 1H), 8.26 (d, J = 9.2 Hz, 1H). MS (ESI) m/z 494.21
2
2
dried by Na SO , and concentrated in vacuo. The residue
2
4
was chromatographed on silica, eluting with ether/CH Cl2
2
(
15:1–5:1 gradient) to give the compound (a1) as yellow pow-
1
+
der solid (yield 77%). m.p.: 117-118 °C. H NMR (500 MHz,
[M + H] . Anal. Calcd. for C H NO C 85.17, H 5.51, N
3
5
27
2:
CDCl , δ, ppm): 1.49 (s, 12H, CH ), 7.99–9.09 (m, 9H, Ar-
2.84. Found: C 85.11, H 5.57, N 2.89.
3
3

J Fluoresc
Preparation of 1,6-Bis[4-(7-N,N
The preparation of b3 was similar to that described
−
1
′-Diethylaminocoumarin-3-Yl)Phenyl]Pyrene (b2)
for b2. m.p.: >280 °C. IR (KBr pellet, cm ): 1712 (ν
C=O), 1590 (ν ), 1520 (ν Ar C=C), 1131 (ν C-O-C),
C=C
1
Compound a3 was obtained from the reaction of 3-(4-
Bromophenyl)-7-(N,N′-diethylamino) coumarin and
bis(pinacolato)diboron [16].
823 (ν Ar C-H). H NMR (400 MHz, CDCl ) δ: 1.25 (t,
3
12H), 3.46 (q, J = 6.7 Hz, 8H), 6.68–6.58 (m, 4H),
7.43–7.32 (m, 6H), 7.55 (d, J = 8.1 Hz, 4H), 7.79 (dd,
J = 6.9, 3.1 Hz, 4H), 7.92 (s, 2H), 7.96 (d, J = 8.1 Hz,
Under N atmosphere, 1,6-dibromopyrene (4.7 g, 11 mol),
2
+
Compound a3 (1 g, 2.8 mmol), TBAB (0.18 g, 0.06 mmol) and
4H). MS (ESI) m/z 761.34 [M + H] . Anal. Calcd. for
(
PPh ) Pd(0) (0.25 g, 0.22 mmol) were dissolved in the mix-
C H N O : C 82.08, H 5.83, N 3.68. Found: C 82.11,
52 44 2 4
3
4
ture of 40 mL toluene and 10 mL 2 M Na CO solution. The
H 5.87, N 3.69.
2
3
mixture was stirred under reflux at 120 °C for 24 h. After
cooling to room temperature, yellow precipitate was produced.
The precipitate was filtered, rinsed with ethanol four times and
then dissolved in dichloromethane, washed with water (3 ×
Crystallography
A single crystal of b1 obtained from CH Cl solution was
2
2
2
0 mL). The combined organic layer was dried by anhydrous
selected for data collection that was performed on Bruker
Smart Apex CCD diffractometer equipped with graphite-
monochromatic Mo Kα radiation (λ = 0.71073 Å) at
293 K. The structure was solved by direct methods and
refined by full-matrix least-squares method on F using
SHELXL.
Na SO and concentrated under reduced pressure. The residue
was chromatographed on silica, eluting with dichloromethane/
ethylacetate (50:1) to give yellow powder product of b2 in 76%
yield. m.p.: >280 °C. IR (KBr pellet, cm ): 1717 (ν
2
4
−1
2
), 1618
C=O
1
(ν C=C), 1519 (ν Ar C=C), 1130 (ν C-O-C), 848 (ν Ar C-H). H
NMR (600 MHz, CDCl ) δ: 8.28 (d, J = 9.1 Hz, 2H), 8.23 (d,
Single crystals of b2 and b3 have not obtained.
3
J = 8.0 Hz, 2H), 8.07 (d, J = 8.7 Hz, 2H), 8.03 (d, J = 7.6 Hz,
2
4
2
H), 7.93 (d, J = 7.9 Hz, 4H), 7.87 (s, 2H), 7.72 (d, J = 7.8 Hz,
H), 7.39 (d, J = 8.8 Hz, 2H), 6.66 (d, J = 8.1 Hz, 2H), 6.60 (s,
OLEDs Fabrication and Characterization
H), 3.47 (dd, J = 13.9, 6.7 Hz, 8H), 1.26 (t, J = 7.1 Hz, 12H).
To investigate the EL properties of b1 as the emitter, the
vacuum-processed doped device with a configuration of
ITO/TAPC (20 nm)/TBADN: Dopant (x wt%, 30 nm)/
TPBi (50 nm)/Liq (2 nm)/Al (150 nm) was fabricated.
(ITO: Indium tin oxide; TAPC: 1,1-bis-(4-bis(4-
methylphenyl)-amino- phenyl)-cyclohexane; TBADN:
+
MS (ESI) m/z 785.34 [M + H] . Anal. Calcd. for C H N O :
C 82.63, H 5.65, N 3.57. Found: C 82.66, H 5.67, N 3.59.
54 44 2 4
Preparation of 9,10-Bis[4-(7-N,N
′-Diethylaminocoumarin-3-Yl)Phenyl]Anthracene (b3)
9
,10-bis(2-naphthyl)-2-t-butylan-thracene; TPBI: 2,2′,2″-
9
,10-Dibromoanthracene was obtained by the reaction of an-
(1,3,5- Benzinetriyl)-tris(1-phenyl-1-H-benzimidazole)).
In the device, indium tin oxide (ITO) was used as the an-
ode, TAPC was used as hole transporting layer, TPBi was
thracene and NBS according to the method described by lit-
erature [17].
Fig. 1 Schematic diagram of the
OLED device configuration
(upper left), the corresponding
HOMO and LUMO energy levels
of the materials used in the work
(
upper right) and structures of
TAPC, TBADN and TPBi
bottom)
(

J Fluoresc
Table 1 Crystal data and
structure refinement for b1
Empirical formula
Formula weight
35 2
C H27NO
493.58
298(2)
0.71073
Temperature (K)
Wavelength (Å)
Crystal system, space group
Unit cell dimensions
Triclinic, P-1
a = 9.4154(6) Å α = 73.0530(10) °
b = 10.5549(8)Å β = 82.787(2) °
c = 13.5693(11) Å γ = 78.9830(10) °
1262.66(16)
3
Volume (Å )
3
Z, Calculated density (Mg/m )
2, 1.298
−1
Absorption coefficient (mm )
F(000)
0.080
520
Crystal size (mm)
0.45 × 0.40 × 0.21
Theta range for data collection (°)
Limiting indices
2.62 to 25.02
-10 ≤ h ≤ 11, −12 ≤ k ≤ 12, −16 ≤ l ≤ 9
6408 / 4378 [R(int) = 0.0266]
98.1%
Reflections collected / unique
Completeness to theta = 25.02
Absorption correction
Max. and min. Transmission
Refinement method
Semi-empirical from equivalents
0.9834 and 0.9650
2
Full-matrix least-squares on F
Data / restraints / parameters
4378 / 0 / 385
1.033
2
Goodness-of-fit on F
Final R indices [I > 2σ(I)]
R
R
1
= 0.0513, wR
2
= 0.1057
R indices (all data)
1
= 0.1091, wR
2
= 0.1196
−3
Largest diff. Peak and hole (eÅ )
0.174 and − 0.202
used as the electron transport and hole/exciton-blocking
layer, Liq was used as electron injection layer, and Al
was used as the cathode, respectively. The codeposited
mixture of TBADN and different concentration of b1 was
served as the emitting layer. The device configuration (up-
per left), the corresponding HOMO and LUMO energy
levels of the materials used in the work (upper right) and
structures of TAPC, TBADN and TPBi (bottom) are
depicted in Fig. 1.
phenyl group and pyrene skeleton is 59.67 °, and the dihedral
angle between coumarin ring and phenyl group is 40.29 °.
As shown in Fig. 3, there are three intramolecular nonclas-
sical C29-H29…O2, C35-H35C…Cg1, C35-H35B…Cg2
hydrogen bonds to assemble four adjacent molecules in the
crystal packing of b1. These C–H···π stacking interactions are
present between CH groups and aromatic rings with H···π
distance of 2.864 Å and 2.867 Å for C35-H35C···Cg1 and
C35-H35B···Cg2, respectively, in which Cg1 is the centroid
Table 2 Selected bond lengths and angles for b1
Bond lengths [Å]
Bond angles [°]
Results and Discussion
N(1)-C(7)
N(1)-C(32)
N(1)-C(34)
O(1)-C(5)
O(1)-C(1)
O(2)-C(1)
C(2)-C(10)
C(13)-C(16)
1.368(3)
1.504(12)
1.551(16)
1.377(3)
1.386(3)
1.221(3)
1.488(3)
1.500(3)
C(7)-N(1)-C(32)
C(7)-N(1)-C(34)
C(32)-N(1)-C(34)
C(5)-O(1)-C(1)
O(2)-C(1)-O(1)
O(2)-C(1)-C(2)
O(1)-C(1)-C(2)
O(1)-C(5)-C(4)
N(1)-C(7)-C(8)
N(1)-C(7)-C(6)
119.3(4)
118.7(4)
121.9(5)
122.9(2)
114.8(2)
127.2(2)
118.0(2)
120.0(2)
121.3(3)
121.3(3)
X-Ray Crystallographic Analyses
The crystal data and experimental details of compound b1 are
shown in Table 1. The selected bond lengths and bond angles
of b1 are listed in Table 2.
The molecular structure of b1 is shown in Fig. 2. The crystal
belongs to Triclinic space group P-1, a = 9.4154(6) Å, b =
1
8
0.5549(8) Å, c = 13.5693(11) Å, α = 73.0530(10) °, β =
3
2.787(2) °, γ = 78.9830(10) °, U = 1262.66(16) Å , Z = 2,
3
−1
Dc = 1.298 Mg/m , μ = 0.080 mm . The dihedral angle between

J Fluoresc
Fig. 2 ORTEP drawing of the
molecular structure of b1 along
with the atomic abeling scheme
Fig. 3 Illustration of hydrogen
bond interactions in molecular
structure of b1
for the C4/C5/C6/C7/C8/C9 ring and Cg2 is the centroid for
C20/C21/C22/C23/C24/C25 ring. In addition, C29-H29···O2
quantum yield (Φ), fluorescent lifetime (τ) and molar extinc-
tion coefficient (ε), and CIE of the tested compounds.
(
2.687 Å) bond is present to connected two other molecules.
The crystallographic data (excluding structure factors) of
The strong absorption bands of b1-b3 are at the 407–
414 nm, which correspond to the π-π* absorption induced
by the larger conjugative polycyclic aromatic hydrocarbons
groups. These compounds exhibit blue fluorescence with
emission peaks in CH Cl cover the 470–480 nm region with
compound b1 has been deposited with the Cambridge
Crystallographic Center as supplementary publication no.
CCDC 1489715.
2
2
little difference.
In diluted chloroform solution, coumarin has two absorp-
tion peaks at 281 and 320 nm, and the emission peak at
Photophysical Properties
4
30 nm [18]. Compared with coumarin, the bathochromic
The UV-vis absorption and photoluminescence spectra of test-
ed compounds in dilute chloroform solutions are presented in
Fig. 4. Table 3 lists the UV-vis absorption maxima (λa,max),
emission maxima (λem,max), Stokes shift (Δλ), fluorescent
shifts are found, which is due to the larger plane conjugation
and the increased number of diethylamino coumarin group,
because diethylamino-substitution with electron-donating
ability at 7-position of coumarin may increase π-conjugation.
It is also found from Table 3 that compound b2 has the
highest fluorescence quantum yield and molar extinction co-
efficient. These three compounds have similar CIE values.
1
0
0
0
0
0
.0
.8
.6
.4
.2
.0
1.0
0.8
0.6
0.4
0.2
0.0
b1
b2
b3
Thermal Properties
Thermogravimetric analysis (TGA) measurement was per-
formed in flowing dry nitrogen atmosphere at the heating rate
−1
of 10 °C·min . The results of TGA measurement of tested
compounds are shown in Fig. 5. Compound b1 containing one
coumarin group displays the lowest thermal stability, that
shows less 2% weight loss at 400 °C. At 430 °C, there is a
sharp weight loss in its TGA curve, indicating b1 begins to
decompose at this temperature. The decompose temperature
of the b2 and b3 are closed due to their similar molecular
3
00
400
500
600
Wavelength(nm)
Fig. 4 UV–vis absorption spectra and photoluminescence emission
spectra of compounds in chloroform solutions (C = 1.0 × 10− mol/L)
5

J Fluoresc
Table 3 Photophysical and
electrochemical properties of b1,
b2 and b3
Compound
λ
nm
a,max
λ
nm
e,max
Δλ
nm
Φ %
τ
ns
ε
CIE
(x,
y)
E
eV
HOMO
E
eV
LUMO
Eg
eV
−1
−1
L∙mol ∙cm
5
(×10 )
b1
b2
b3
407
474
67
62
57
83.11
89.31
86.32
8.84
8.46
8.90
8.44
8.94
8.62
(0.13,
−5.04
−2.31
−2.37
−2.35
2.73
2.71
2.75
0
2
5
.-
-
)
414
414
476
471
(0.13,
−5.08
−5.10
0
2
6
.-
-
)
(0.13,
0
2
1
.-
-
)
structures with two coumarin groups. Compound b2 shows
% weight loss at 450 °C, and sharp weight loss at 460 °C.
4.8 eV below the vacuum level. The ionization potential (IP) may
be regarded as HOMO energy level, and the electron affinity (EA)
2
Compound b3 shows 2% weight loss at 440 °C, and sharp
weight loss at 450 °C. The results indicate that compounds of
b1, b2 and b3 meet with the thermal stability requirement of
fabrication of OLED luminescence.
may be regarded as LUMO energy level [19, 20]. The E repre-
sent the band gap between HOMO and LUMO, and the value can
g
calculated from optical absorption edge. The overall EHOMO
,
ELUMO, and E data of the compounds were listed in Table 3.
g
Electroluminescence Properties
Electrochemical Properties
The current density-voltage-luminance (I-V-L) characteristics,
current/power efficiency versus luminance curves and exter-
nal quantum efficiency (EQE) for the devices based on b1
with different dopant concentrations are shown in Fig. 7. As
shown in Fig. 7, the devices fabricated from b1 exhibit the
Cyclic voltammetry (CV) was employed to evaluate redox
potentials and molecular orbital energy levels. The informa-
tion on HOMO and LUMO of the emitting layer are important
for designing optimized device structures. The cyclic voltam-
mograms of b1, b2 and b3 are shown in Fig. 6.
The HOMO energy level, the electrochemical gap (Eg) and
the LUMO energy level, can be calculated by the following
relations:
2
maximum brightness of 4732, 7025, 8165 and 7712 cd/m at
4
wt%, 7 wt%, 10 wt% and 13 wt% doping concentrations,
respectively. The maximum luminous efficiencies of 4.28,
.59, 6.02 and 6.13 cd/A were observed in the devices with
4
Â
Ã
OX
þ
different doping concentrations. By comparing the device per-
formances of the different doping concentrations, the maxi-
EHOMO ¼ − E −EðFc=Fc Þ þ 4:8 eV
Eg ¼ hc=λabs ¼ 1240=λabs
ELOMO ¼ EHOMO−Eg
2
mum brightness of 8165 cd/m at 12.36 V and the maximum
2
luminous efficiencies of 6.02 cd/A at 851.6 cd/m was obtain-
ox
+
where E is the oxidation onset, E (F /F ) is the ferrocene half-
C
C
ed for the device with 10 wt% doping concentration, and the
+
wave potential. The energy level of the Fc /Fc is assumed to be
1
00
b1
b2
b3
8
6
4
2
0
0
0
0
0
100
200
300
400
500
600
700
o
Temperature ( C)
Fig. 5 Thermogravimetric analyses (TGA) of b1, b2 and b3
Fig. 6 Cyclic voltammogram curves of b1, b2 and b3

J Fluoresc
Fig. 8 EL spectra of devices based on b1 with different dopant
concentrations (spectra were measured at the same current density in ca.
−
2
2
0 mA∙cm )
Conclusion
Three anthracen- or pyrene-based coumarin derivatives were
successfully synthesized and the photophysical properties
have been carried out. These coumarin derivatives exhibit
excellent thermal stabilities and high photoluminescence
quantum efficiencies in dichloromethane solutions. The re-
sults indicate that the high π-conjugated molecule structure
enhance the light absorption and the strong blue emission
abilities of b1, b2 and b3 due to the contribution of anthra-
cene, pyrene and 7-(N,N′-diethylamino)-3-(phen-2-
yl)coumarin groups. The vacuum processed doped devices
with a configuration of ITO/TAPC (20 nm)/TBADN: b1 (x
wt%, 30 nm)/TPBi (50 nm)/Liq (2 nm)/Al (150 nm) was fab-
ricated. The devices with b1 (10 wt%) displayed the perfor-
2
mance with the maximum brightness of 8165 cd/m , the max-
imum luminous efficiencies of 6.13 cd/A and the maximum
external quantum efficiency (EQE) of 2.75%.
The devices fabricated from b2 and b3 have being made
and investigated. Based on the photophysical properties of b2
and b3, it is deduced that the devices of b2 and b3 perform
better electroluminescence properties.
Fig. 7 I-V-L characteristics (a), luminance-efficiency (b) and external
quantum efficiency (c) for the devices based on b1 with different
dopant concentrations
Acknowledgements This work was financially supported by the Gansu
Universities Research Foundation (2015A-066), Gansu Natural Science
Foundation (1606RJZA018), the National Natural Science Foundation of
China (Grand 51563014) and the Instrument Analysis center of Lanzhou
Jiaotong University.
maximum external quantum efficiency (EQE) of 2.76% was
obtained at same doping concentration.
Figure 8 shows the electroluminescence spectra of the b1
with different dopant concentrations. The devices fabricated
from b1 display blue emission with a maximum peak at
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Highly sensitive and reusable mercury (II) sensor based