Y. Yu et al.
Dyes and Pigments 180 (2020) 108511
�
high-performance deep-blue emitters in OLEDs.
POCl
3
(9.4 mL, 102.0 mmol) was added dropwise to the mixture at 0 C.
After mixing, the temperature was raised to room temperature, during
which the color of the solution turned red. The reaction mixture was
2
. Experimental
�
then heated to 60 C and stirred for an additional 2 h. The product
2
.1. Materials and measurement
mixture was poured into an ice-bath and neutralized with sodium bi-
carbonate. After filtration, the residure was dried over P
2
O
5
in a vacuum
Cl as the
All the reagents and solvents used for the synthesis were purchased
drier, then purified by column chromatography using CH
2
2
�
from Aldrich or Acros companies and used as received. All reactions
eluent. Yellow solid (6.4 g, 90%). MP: 143 C. IR data (KBr): 1694, 1587,
1505, 1493, 1426, 1392, 1331, 1292, 1217, 1167, 1112, 822, 762, 701
1
were performed under a dry nitrogen atmosphere. The H NMR spectra
À 1
1
were recorded on AVANCZ 500 spectrometers at 298 K by utilizing
cm . H NMR (500 MHz, DMSO) δ 9.88 (s, 2H), 7.84 (d, J ¼ 8.7 Hz,
4H), 7.47 (t, J ¼ 7.9 Hz, 2H), 7.31 (t, J ¼ 7.4 Hz, 1H), 7.24–7.20 (m, 2H),
7.17 (d, J ¼ 8.6 Hz, 4H). HRMS (ESI) m/z: [M þ H]þ calcdfor
3
deuterated chloroform (CDCl ) or dimethyl sulphoxide (DMSO) as sol-
vent and tetramethylsilane (TMS) as standard. The compounds were
characterized by Flash EA 1112, CHNS–O elemental analysis instru-
ment. The HRMS (ESI) mass spectra were recorded using a Bruker
micrOTOF-Q II instrument. UV–vis absorption spectra were recorded on
UV-3100 spectrophotometer. Fluorescence measurements were carried
out with RF-5301PC. Thermal gravimetric analysis (TGA) was under-
taken on a PerkinElmer thermal analysis system at a heating rate of 10
C
20
H16NO
2
: 302.1173, found 302.1176.
0
00
2.3.3. 4,4 ,4 -nitrilotribenzaldehyde (M3)
M2 (2.4 g, 8.2 mmol) was dissolved in 8 mL DMF (8 mL). POCl
3
�
(10.0 mL, 100.0 mmol) was added dropwise to the mixture at 0 C. After
mixing, the temperature was raised to room temperature, during which
the color of the solution turned red. The reaction mixture was then
�
À 1
À 1
C min and a nitrogen flow rate of 80 mL min . The differential
scanning calorimeter (DSC) analysis was determined using a NETZSCH
�
heated to 60 C and stirred for an additional 2 h. The product mixture
�
À 1
(
DSC-204) instrument at 10 C min under nitrogen flushing. Cyclic
was poured into an ice-bath and neutralized with sodium bicarbonate.
voltammetry (CV) were performed with a BAS 100 W Bioanalytical
After filtration, the residure was dried over P
2
O
5
in a vacuum drier, then
Cl as the eluent. Yellow
Systems, using a glass carbon disk (Φ ¼ 3 mm) as working electrode,
purified by column chromatography using CH
2
2
þ
�
platinum wire as auxiliary electrode with porous ceramic wick, Ag/Ag
solid (2.1 g, 80%). MP: 245 C. IR data (KBr):1694, 1589, 1504, 1434,
À 1
1
as reference electrode, standardized for the redox couple ferricinium/
ferrocene. All solutions were purged with nitrogen stream for 10 min
before measurement. The procedure was performed at room tempera-
ture and nitrogen atmosphere was maintained over the solution during
measurements.
1392, 1322, 1275, 1217, 1168, 819, 724 cm
. H NMR (500 MHz,
DMSO) δ 9.94 (s, 3H), 7.91 (d, J ¼ 8.5 Hz, 6H), 7.28 (d, J ¼ 8.5 Hz, 6H).
HRMS (ESI) m/z: [M þ H]þ calcdfor C21
3
H16NO : 330.1115, found
330.1125.
2
.3.4. N,N-diphenyl-4-(1-phenyl-1H-phenanthro[9,10-d]imidazole-2-yl)
2
.2. Device fabrication
aniline (TPA-1PI)
A mixture of aniline (5.0 mmol, 465 mg), phenanthrenequinone (1.0
mmol, 208.0 mg), intermediate M1 (1.0 mmol, 237.0 mg), ammonium
acetate (4.0 mmol, 308.0 mg), and acetic acid (8 mL) was refluxed under
nitrogen in an oil bath. After 2 h, the mixture was cooled and filtered.
The solid product was washed with an acetic acid/water mixture (15
The EL devices were fabricated by vacuum deposition of the mate-
À 6
À 1
rials at 10 Torr onto ITO glass with a sheet resistance of 25 Ω square
.
-
1
All of the organic layers were deposited at a rate of 1.0 Å . The cathode
was deposited of LiF (1 nm) at a deposition rate of 0.1 Å-1 and then
capping with Al metal (100 nm) through thermal evaporation at a rate of
mL, 1:1) and water. And then, it was purified by chromatography using
-
1
�
4
.0 Å . The electroluminescent (EL) spectra and Commission Inter-
CH
2
Cl
2
as eluent. white solid (483.0 mg, 90%). MP: 285 C. IR data
nationale De L’Eclairage (CIE) coordinations of these devices were
measured by a PR650 spectroscan spectrometer. The luminance-current
and density-voltage characteristics were recorded simultaneously with
the measurement of the EL spectra by combining the spectrometer with
a Keithley model 2400 programmable voltage-current source. All mea-
surements were carried out at room temperature under ambient
conditions.
(KBr): 1588, 1516, 1485, 1468, 1453, 1424, 1383, 1330, 1281, 1195,
À 1
1
1076, 1037, 966, 840, 747, 735, 720 cm . H NMR (500 MHz, DMSO) δ
8.92 (d, J ¼ 7.9 Hz, 1H), 8.87 (d, J ¼ 8.3 Hz, 1H), 8.67 (d, J ¼ 7.9 Hz,
1H), 7.77 (t, J ¼ 7.5 Hz, 1H), 7.70–7.64 (m, 1H), 7.57–7.51 (m, 1H),
7.47 (d, J ¼ 8.8 Hz, 2H), 7.39–7.29 (m, 4H), 7.11 (t, J ¼ 7.4 Hz, 2H),
7.05 (t, J ¼ 7.7 Hz, 4H), 6.83 (d, J ¼ 8.8 Hz, 2H). HRMS (ESI) m/z: [M þ
H]þ calcdfor C39
28 3
H N : 538.2278, found 538.2278.
2
.3. Synthesis
2.3.5. N-phenyl-4-(1-phenyl-1H-phenanthro[9,10-d]imidazole-2-yl)-N-(4-
(
1-phenyl-1H-phenanthro[9,10-d]imidazole-2-yl)phenyl)aniline (TPA-2PI)
2
.3.1. 4-(diphenylamino)benzaldehyde (M1)
A mixture of aniline (10.0 mmol, 930.0 mg), phenanthrenequinone
Triphenylamine (5.0 g, 20.3 mmol) was dissolved in DMF (10 mL).
(2.0 mmol, 516.0 mg), intermediate M2 (1.0 mmol, 301.0 mg), ammo-
nium acetate (8.0 mmol, 616.0 mg), and acetic acid (8.0 mL) was
refluxed under nitrogen in an oil bath. After 2 h, the mixture was cooled
and filtered. The solid product was washed with an acetic acid/water
mixture (15 mL, 1:1) and water. And then, it was purified by chroma-
�
POCl (1.9 mL, 20.3 mmol) was added dropwise to the mixture at 0 C.
3
After mixing, the temperature was raised to room temperature, during
which the color of the solution turned red. The reaction mixture was
�
then heated to 60 C and stirred for an additional 2 h. The product
mixture was poured into an ice-bath and neutralized with sodium bi-
tography using CH
2
Cl
2
as eluent. White solid (730.4 mg, 88%). MP: 362
�
carbonate. After filtration, the residure was dried over P
2
O
5
in a vacuum
Cl as the
C. IR data (KBr): 1738, 1597, 1536, 1514, 1494, 1471, 1453, 1382,
À 1
1
drier, then purified by column chromatography using CH
2
2
1344, 1320, 1286, 1265, 1183, 1073, 1037, 920, 837, 754, 723 cm . H
NMR (500 MHz, DMSO) δ 8.92 (d, J ¼ 8.3 Hz, 2H), 8.87 (d, J ¼ 8.3 Hz,
2H), 8.68 (d, J ¼ 7.9 Hz, 2H), 7.81–7.65 (m, 14H), 7.57–7.52 (m, 2H),
7.51 (d, J ¼ 8.8 Hz, 4H), 7.35 (dt, J ¼ 15.5, 8.1 Hz, 4H), 7.17 (t, J ¼ 7.4
Hz, 1H), 7.06 (t, J ¼ 8.7 Hz, 4H), 6.90 (d, J ¼ 8.8 Hz, 4H). HRMS (ESI)
�
eluent. Pale yellow solid (5.4 g, 96%). MP: 120 C. IR data (KBr): 1693,
1
592, 1503, 1430, 1392, 1322, 1290, 1217, 1168, 820, 710, 650, 532
À 1
1
cm . H NMR (500 MHz, DMSO) δ 9.77 (s, 1H), 7.72 (d, J ¼ 8.7 Hz,
2
2
2
H), 7.42 (t, J ¼ 7.8 Hz, 4H), 7.28–7.15 (m, 6H), 6.89 (d, J ¼ 8.7 Hz,
H). HRMS (ESI) m/z: [M þ H]þ calcdfor C19
H16NO: 274.1217, found
m/z: [M þ H]þ calcdfor C60
40 5
H N : 830.3277, found 830.3278.
74.1226.
2
.3.6. tris(4-(1-phenyl-1H-phenanthro[9,10-d]imidazole-2-yl)phenyl)
amine (TPA-3PI)
A mixture of aniline (15.0 mmol, 1.4 g), phenanthrenequinone (3.0
2
.3.2. 4,4’-(phenylazanediyl)dibenzaldehyde (M2)
Triphenylamine (5.0 g, 20.3 mmol) was dissolved in DMF (10 mL).
2