Page 7 of 10
Journal Name
RSC Advances
DOI: 10.1039/C5RA07161E
n
ꢀBu4NPF6 as a supporting electrolyte in CH2Cl2 under argon brine solution (50 ml), dried over anhydrous Na2SO4, filtered
flow. Melting points were measured using an Electrothermal IA and removed to dryness. Purification by column
9100 series of digital melting point instrument and are chromatography over silica gel eluting with a mixture of
uncorrected. Highꢀresolution mass spectrometry (HRMS) CH2Cl2 and hexane (1:4) followed by recrystallization with a
analysis was performed on an Autoflex II MALDIꢀTOF/TOF mixture of CH2Cl2 and CH3OH yielded:
o
1
mass spectrometer. The atomic force microscopy (AFM) G1PYR as light green solids (90%): m.p. 200 C; H NMR
analysis was performed on an XE 100.
(300 MHz, CDCl3)
δ 8.41 (2H, s), 8.34 (2H, d, J = 9.30 Hz),
All calculations were performed by Gaussian 09 code in
CH2Cl2 solvent.26 The energy or geometry optimizations were
done by B3LYP/6ꢀ31G(d,p) method. The ground to excited
state excitation energies were calculated by TDꢀB3LYP/6ꢀ
31G(d,p) in CH2Cl2.
8.25 (2H, d, J = 7.80 Hz), 8.20ꢀ8.10 (10H, m), 8.06ꢀ7.97 (4H,
m), 7.79 (2H, d, J = 8.40 Hz), 7.66 (2H, d, J = 7.64 Hz), 4.47
(2H, t, J = 7.20 Hz), 2.06 (2H, q, J = 6.90 Hz), 1.57ꢀ1.30 (18H,
m), 0.91 (3H, t, J = 6.90 Hz) ppm; 13C NMR (300 MHz,
CDCl3)
δ 140.31, 138.68, 132.10, 131.58, 131.10, 130.29,
128.89, 128.76, 128.25, 127.51, 127.32, 127.17, 125.93,
125.74, 125.11, 125.04, 124.93, 124.66, 123.11, 122.48,
108.71, 43.55, 31.96, 30.93, 29.69, 29.55, 29.40, 29.25, 27.50,
22.73, 14.16 ppm; MALDIꢀTOF (m/z) (M+) calcd for C56H49N:
735.3865, found 735.2479.
Materials synthesis
3,6ꢀBIS
(
CARBAZOL
ꢀ
N
′ꢀYL)ꢀ
N
ꢀ
DODECYLCARBAZOLE (2):
A
mixture of
1
(2.00 g, 4.04 mmol), carbazole (1.49 g, 8.89
mmol), CuI (0.38 g, 2.02 mmol), K3PO4 (2.14 g, 10.10 mmol)
and ±transꢀ1,2ꢀdiaminocyclohexane (0.23 g, 2.10 mmol) in
toluene (50 ml) was stirred at refluxed under N2 for 24 h. After
cooling, water (30 ml) was added and the mixture was extracted
with CH2Cl2 (50 ml x 2). The combined organic phase was
washed water (50 ml x 2), brine solution (50 ml), dried over
anhydrous Na2SO4, filtered and removed to dryness.
Purification by column chromatography over silica gel eluting
with a mixture of CH2Cl2 and hexane (1:4) followed by
recrystallization with a mixture of CH2Cl2 and CH3OH afforded
the product (2.15 g, 80%) as colorless solids: m.p. 232 C; H
NMR (300 MHz, CDCl3) 8.26 (2H, s), 8.21 (4H, d, J = 7.80
Hz), 7.68 (4H, s), 7.47ꢀ7.41 (8H, m), 7.36ꢀ7.28 (4H, m), 4.49
(2H, t, J = 7.20 Hz), 2.06 (2H, t, J = 6.90 Hz), 1.56ꢀ1.33 (18H,
m), 0.93 (3H, t, J = 6.30 Hz) ppm; 13C NMR (300 MHz,
o
1
G2PYR as light green solids (91%): m.p. >250 C; H NMR
(300 MHz, CDCl3) 8.49 (6H, s), 8.33 (4H, d, J = 9.3 Hz),
δ
8.22 (4H, d, J = 7.8 Hz), 8.19ꢀ8.05 (20 H, m), 8.02 (4H, d, J =
3.0 Hz), 7.98 (4H, d, J = 7.8 Hz), 7.88 (2H, d, J = 8.4 Hz),
7.80ꢀ7.74 (6H, m), 7.68 (4H, d, J = 8.4 Hz), 4.55 (2H, bs), 2.11
(2H, bs), 1.48 (2H, bs), 1.27 (16H, bs), 0.86 (3H, t, J = 6.6 Hz)
ppm; 13C NMR (300 MHz, CDCl3)
δ 141.80, 140.45, 138.57,
133.09, 131.55, 131.06, 130.34, 129.40, 129.07, 128.89,
128.20, 127.48, 127.37, 127.19, 126.05, 125.92, 125.68,
125.07, 125.00, 124.94, 124.68, 124.64, 123.62, 123.46,
122.42, 119.97, 110.39, 109.84, 43.83, 31.92, 30.92, 29.66,
29.63, 29.53, 29.36, 29.26, 27.49, 22.69, 14.11 ppm; MALDIꢀ
TOF (m/z) (M+) calcd for C112H79N3: 1465.6274, found
1465.5541.
o
1
δ
o
1
G1TPA as white solids (89%): m.p. 200 C; H NMR (300
CDCl3)
δ 141.91, 129.35, 125.98, 125.87, 123.15, 120.29,
MHz, CDCl3) 8.36 (2H,s ), 7.73 (2H, dd, J = 8.40 Hz, J = 1.2
δ
119.86, 110.13, 109.77, 43.15, 31.94, 29.67, 29.61, 29.51,
Hz), 7.64 (2H, d, J = 8.40 Hz), 7.47 (2H, d, J = 8.40 Hz), 7.33ꢀ
7.28 (8H, m), 7.24ꢀ7.18 (12H, m), 7.07 (4H, t, J = 7.20 Hz),
4.34 (2H, t, J = 7.20 Hz), 1.93 (2H, q, J = 6.90 Hz), 1.52ꢀ1.29
(18H, m), 0.90 (3H, t, J = 6.90 Hz) ppm; 13C NMR (300 MHz,
29.38, 29.21, 27.46, 22.86, 14.29 ppm; MALDIꢀTOF (m/z
)
(M+) calcd for C48H47N3: 665.9069, found 665.4128.
3,6ꢀBIS(3′,6′ꢀDIBROMOCARBAZOL
ꢀN′ꢀYL)ꢀNꢀ
DODECYLCARBAZOLE (3): To a stirred solution of
2
(1.00 g,
CDCl3)
δ 147.92, 146.43, 140.24, 136.51, 131.94, 129.27,
1.50 mmol) in THF (60 ml) in the dark was added NBS (1.10 g,
6.16 mmol) in small portions. The mixture was allowed to stir
for 5 h. Water (15 ml) was added and the mixture was extracted
with CH2Cl2 (50 ml x 2). The combined organic phase was
washed with bine solution (50 ml), dried over anhydrous
Na2SO4, filtered and removed to dryness. Purification by
127.92, 125.10, 124.99, 124.54, 124.22, 123.56, 122.71,
118.48, 109.06, 43.37, 31.95, 29.74, 29.55, 29.46, 29.36, 29.10,
27.37, 22.72, 14.15 ppm; MALDIꢀTOF (m/z) (M+) calcd for
C60H59N3: 821.4709, found 821.1257.
o
1
G2TPA as white solids (85%). m.p. >250 C; H NMR (300
column chromatography over silica gel eluting with a mixture MHz, CDCl3)
δ
8.39 (4H, s), 8.30 (2H, s), 7.72 (6H, s), 7.65ꢀ
of CH2Cl2 and hexane (1:4) followed by recrystallization with a 7.60 (12H, m), 7.45 (6H, d, J = 8.40 Hz), 7.30ꢀ7.25 (16H, m),
mixture of CH2Cl2 and CH3OH gave the product (1.43 g, 98%) 7.20ꢀ7.15 (20H, m), 7.03 (8H, t, J = 7.20 Hz), 4.52 (2H,t, J =
o
1
7.20 Hz), 2.16ꢀ2.06 (2H, m), 1.61ꢀ1.26 (18H, m), 0.89 (3H, t,
J
as white solids: m.p. 150 C; H NMR (300 MHz, CDCl3)
δ
8.21 (4H, s), 8.16 (2H, s), 7.68 (2H, d, J = 8.70 Hz), 7.57 (2H,
=
6.90 Hz) ppm; 13C NMR (300 MHz, CDCl3)
δ
147.85,
d, J = 8.70 Hz), 7.48 (4H, d, J = 8.55 Hz), 7.22 (4H, d, J = 146.49, 141.58, 140.25, 136.37, 132.88, 130.87, 129.36,
8.70 Hz), 4.49 (2H, t, J = 7.20 Hz), 2.04 (2H, t, J = 6.90 Hz), 123.223, 128.81, 127.93, 125.84, 125.26, 124.45, 124.20,
1.57ꢀ1.27 (18H, m), 0.87 (3H, t, J = 6.30 Hz) ppm; 13C NMR 123.83, 123.45, 122.69, 119.70, 118.39, 110.10, 43.79, 38.76,
31.92, 30.90, 30.39, 29.70, 29.65, 29.36, 28.94, 27.45, 23.77,
22.98, 22.69, 14.11 ppm; MALDIꢀTOF (m/z) (M+) calcd for
C120H99N7: 1637.7962, found 1637.4813.
(300 MHz, CDCl3)
125.78, 123.32, 123.21, 119.72, 112.85, 111.48, 110.45, 43.78,
31.92, 29.64, 29.58, 29.46, 29.35, 29.17, 27.41, 22.69, 14.12
ppm; MALDIꢀTOF
977.0190, found 977.1070.
δ 140.82, 140.45, 129.33, 128.46, 126.61,
(m/z)
(M+) calcd for C48H43Br4N3:
OLED fabrication and testing
S
YNTHESIS OF
G
n
PYR AND
G
n
TPA
(0.61 mmol), pyreneꢀ1ꢀboronic acid or 4ꢀ
(diphenylamino)phenylboronic acid (1.40ꢀ3.10 mmol),
All OLED devices using
transporting layer (THL) and
(EML) with the
G
G
n
PYR and
G
n
TPA as holeꢀ
A mixture of
1 or 3
n
PYR as blue emissive layer
device
structures
of
Pd(PPh3)4 (0.02 mmol) and 2M Na2CO3 solution (7 ml) in THF
(25 ml) was degased with N2 for 5 min. The mixture was
refluxed under N2 for 48 h. After cooling, water (30 ml) was
added and the mixture was extracted with CH2Cl2 (50 ml x 2).
The combined organic layer was washed with water (50 ml),
ITO/PEDOT:PSS/THL(spinꢀcoating)(30ꢀ40
nm)/LiF(0.5 nm):Al(150 nm) and ITO/PEDOT:PSS/EML(spinꢀ
coating)(30ꢀ40 nm)/BCP(40 nm)/LiF(0.5 nm):Al(150 nm) were
nm)/Alq3(50
fabricated and characterized as followed. Thin films of
GnPYR
and TPA were deposited on top of PEDOT:PSS coated ITO
G
n
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