392
J. Li et al. / Dyes and Pigments 96 (2013) 391e396
S
S
N
N
N
N
T-TP
T-TP1
Scheme 1. Chemical structures of the compounds in present study.
spectrometer (400 MHz). Mass spectra were recorded on a GC-Tof MS
Micromass, UK) mass spectrometer for TOF-MS-EI, an MALDI micro
acetate (880 mg, 9 mmol) were dissolved in DMSO (40 ml) in
a Schlenk tube under nitrogen. The tube was sealed under nitrogen
and stirred at 80 C for 6 h. A small amount of the reaction mixture
was added to water, extracted into DCM and then dried over
4
MgSO . The filtrate was evaporated under reduced pressure and the
(
ꢁ
MX (Waters, USA) for MALDI-TOF-MS and HP 1100 LC-MSD (USA)
mass spectrometer. The UVevis absorption and fluorescence spectra
measurements were recorded on a Perkin-Elmer Lambda 35 UVe
Visible spectraphotometer and a Perkin-Elmer LS55 fluorescence
spectrometer, respectively. The fluorescence quantum yields were
residue was purified by column chromatography on silica gel (EA/
petroleum ether) to yield bright white solid, yield 36.8%. TOF-MS-EI
determined against rhodamine B as the standard (
F
¼ 0.99 in ethanol)
27 2
(m/z): calcd. for C26H O B, 382.30 found 382.2110.
[9]. Thermogravimetry analyses (TGA) and differential scanning calo-
rimetry (DSC) measurements were carried out using a Perkin-Elmer
thermogravimeter (Model TGA7) and a Netzsch DSC 204 at a heating
2.3.2. Synthesis of target compound T-TP
In a 100 ml round bottom flask was placed compound TP
(100 mg, 0.132 mmol), compound 1 (260 mg 0.68 mmol) and
ꢁ
ꢀ1
rate of 10 C min under a nitrogen atmosphere, respectively. Cyclic
voltammetry was performed by using a conventional three-electrode
configuration and an electrochemical workstation (BAS 100B, USA) at
3 4
[Pd(PPh ) ] (40 mg, 0.035 mmol) were combined under nitrogen.
Then toluene (6 ml), methanol (2 ml) and K
2 M) were added and the reaction mixture was refluxed at 80
2
CO
3
aqueous (0.8 ml,
ꢀ
1
ꢁ
a scan rate of 50 mV s . A (0.10 MAgNO
3
)/Agelectrode and a platinum
C
wire were used as reference and counterelectrodes. All measurements
were made at room temperature in dichloromethane solutions, with
overnight. The filtrate was evaporated under reduced pressure and
the residue was purified by column chromatography on silica gel
(DCM/petroleum ether) to yield red solid, yield 58%. MS (TOF-MS-
0
.10 M tetra-n-butylammonium hexafluorophosphate (Bu
4 6
NPF ) as
supporting electrolyte.
EI, m/z): calcd. for C110
457.4047 (100%), 1458.4077 (65%). H NMR (400 MHz, (CD
): 7.74 (d, J ¼ 8.0 Hz, 4H, ArH), 7.12 (m, 36H, ArH), 6.99 (m, 24H,
ArH), 6.89 (m, 4H, ArH), 6.85 (d, J ¼ 8.0 Hz, 8H, ArH).
76 2
H N S, 1456.57, found 1456.4016 (80%),
1
1
d
3 2
) SO,
2.2. Device fabrication and measurements
The pre-cleaned ITO glass substrates were treated by UV-ozone
2
.3.3. Synthesis of target compound T-TP1
In a 100 ml round bottom flask was placed Compound TP
for 20 min. A 40 nm thick PEDOT: PSS film was first deposited on
ꢁ
the ITO glass substrates, and baked at 120 C for 40 min in air. The
(
[
200 mg, 0.264 mmol, compound 4 (530 mg 1.16 mmol) and
Pd(PPh ] (80 mg, 0.069 mmol) were combined under nitrogen.
emitting layer was spin-coated from the solution of T-TP or T-TP1 in
chlorobenzene on the top of PEDOT: PSS film. Then the films were
transferred into a vacuum chamber to deposit TPBI layer by vacuum
3 4
)
Then toluene (10 ml), methanol (3 ml) and K
2 M) were added and the reaction mixture was refluxed at 80
overnight. The filtrate was evaporated under reduced pressure and
the residue was purified by column chromatography on silica gel
2
CO
3
aqueous (1.6 ml,
ꢁ
ꢀ
6
C
evaporation with a base pressure less than 10 torr. Finally a thin
layer of LiF (1 nm) and 100 nm of Al were vacuum deposited on top
of organic layers as cathode. The EL spectra, CIE coordinates, and
currentevoltageeluminance characteristics were measured with
computer-controlled Spectrascan PR 705 photometer and a Keith-
ley 236 source-measure-unit. All the measurements were carried
out at room temperature under ambient conditions.
(DCM/petroleum ether) to yield red solid, yield 63%. MS (TOF-MS-
EI, m/z): calcd. For C134 S, 1760.70, found 1760.5852 (75%),
92 2
H N
1
1761.5720 (100%), 1762.5881 (82%). H NMR (400 MHz, CDCl
3
,
d
):
8
.37 (d, J ¼ 8.0 Hz, 4H, ArH), 7.73e7.68 (m, 8H, ArH), 7.65 (d,
J ¼ 8.0 Hz, 4H, ArH), 7.56e7.52 (m, 8H, ArH), 7.44e7.39 (m, 4H, ArH),
.13e7.05 (m, 64H, ArH).
7
2
.3. Synthesis of compounds
The important intermediates 4 [6] and TP [9] were synthesized
3. Results and discussion
and characterized according to the literature methods, as described
in Scheme 2.
3.1. Synthesis and thermal properties
2
.3.1. 4,4,5,5-tetramethyl-2-(1,2,2-triphenylvinyl)-1,3,2-
The chemical structures and synthetic routes for compounds T-
TP and T-TP1 are shown in Schemes 1 and 2, respectively. They
were prepared through typical Suzuki coupling reaction of the
brominated core TP with the corresponding boronic ester 1 and
dioxaborolane (1)
Bromotriphenylethylene (1 g, 3 mmol), bis(pinacolato)diboron
(
2
1.52 g, 6 mmol), Pd(dppf)Cl (110 mg, 0.152 mol) and potassium