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Journal of Materials Chemistry C
Page 2 of 10
ARTICLE
Journal Name
Experimental section
Synthetic section
using a Hitachi UV-vis spectrometer 3900. DTOheI: 1p0h.1o0t3o9lu/Cm9iTnCe0s6c4e2n5cGe
(PL) spectra were acquired on Horiba Fluoromax-4
spectrophotometer. The fluorescence lifetime and absolute
fluorescence quantum yield were obtained by Edinburgh FLS980
steady state fluorimeter equipped with integrating sphere.
Thermogravimetric analysis (TGA) was performed on a Netzsch TG
209F3 thermal analyzer under a nitrogen atmosphere at a heating
rate of 10 °C/min from 30 °C to 790 °C. The energy levels and
electrochemical properties were studied by cyclic voltammetry (CV)
in dichloromethane (DCM) solution and 0.1M tetrabutylammonium
perchlorate as the supporting electrolyte. The single crystal of CzPA-
F-PD was cultured by vapour diffusion of DCM solution and
acetonitrile. Diffraction data were collected on XtaLAB Synergy R,
HyPix diffractometer. The single crystal of CzPA-F-PD was kept at
220.00(13) K during data collection.
All organic chemicals and solvents were received from commercial
sources and used, unless otherwise noted, without further
purification. The synthetic route of CzPA-F-PD is shown in Scheme 1.
The intermediate products of 9-(4-nitrophenyl)-9H-carbazole (1) and
4-(9H-carbazol-9-yl) aniline (2) were synthesized according to
reference.23
CzPA-F-Br. The CzPA-F-Br was synthesized by Ullmann reaction.
The compound of 2 (0.54 g, 2.11 mmol), 2,7-dibromo-9,9-dibutyl-9H-
fluorene (2.76 g, 6.33 mmol), sodium tert-butoxide (NatB) (1.02 g,
10.55 mmol), 1,1'-bis(diphenylphosphino)ferrocene (DPPF) (0.061 g,
0.11 mmol) and Pd2(dba)3 (0.10 g, 0.11 mmol) were added into
toluene (20 mL) and mixed uniformity. Under nitrogen protection,
the mixture was stirred and refluxed at 110 °C for 24 h. After cooling
to room temperature, the reaction mixture was washed by water and
extracted with dichloromethane consecutively. The organic phase
was collected and further dried with anhydrous MgSO4. After rotary OLED fabrication
evaporation of solvent, the residue was purified via column
The OLED were fabricated on ITO glass substrates with a sheet
chromatography by using n-hexane as eluent to give intermediate
products of CzPA-F-Br (0.92 g, yield: 45%). 1H NMR (600 MHz, CDCl3,
δ): 8.15 (d, J = 7.8 Hz, 2H), 7.60 (d, J = 8.1 Hz, 2H), 7.54 – 7.37 (m,
12H), 7.31 (dt, J = 14.8, 7.5 Hz, 4H), 7.24 (s, 2H), 7.20 – 7.09 (m, 2H),
1.90 (m, J = 7.2, 3.0 Hz, 8H), 1.16 – 1.07 (m, 8H), 0.78 – 0.64 (m, 20H).
CzPA-F-PD. The CzPA-F-Br (0.97 g, 1 mmol), 4-pyridineboronic acid
pinacol ester (0.82 g, 4 mmol) and Pd(PPh3)4 (0.06 g, 0.05 mmol) were
added to a mixed solution of toluene (20 ml) and aqueous solution
of K2CO3 (5 mL, 2 M). The mixture was heated at 110 °C and refluxed
under nitrogen protection for 12 h. Then, the reaction was quenched
by water and extracted with dichloromethane. The organic phase
was collected and dried over anhydrous MgSO4. After removing
solvent by rotary evaporation, the residue was purified via column
chromatography. The petroleum ether / ethyl acetate (2:1, v/v) were
used as eluent to afford yellow solid of CzPA-F-PD (0.61 g, yield: 63%).
1H NMR (600 MHz, CDCl3, δ): 8.68 (m, 4H), 8.16 (d, J = 7.7 Hz, 2H),
7.75 (d, J = 7.9 Hz, 2H), 7.69 (d, J = 8.2 Hz, 2H), 7.65 (dd, J = 7.9, 1.7
Hz, 2H), 7.61 – 7.58 (m, 6H), 7.49 (d, J = 8.2 Hz, 2H), 7.46 – 7.42 (m,
4H), 7.39 – 7.36 (m, 2H), 7.33 – 7.29 (m, 4H), 7.21 (dd, J = 8.2, 2.1 Hz,
2H), 2.05 – 1.94 (m, 8H), 1.17 – 1.08 (m, 8H), 0.74 (t, J = 7.4 Hz, 20H).
13C NMR (151 MHz, CDCl3, δ): 155.75, 154.58, 153.19, 151.58, 150.20,
144.89, 143.95, 139.17, 138.87, 134.60, 130.68, 129.03, 128.78,
126.88, 126.70, 126.26, 124.44, 124.08, 123.92, 123.27, 122.78,
resistance of 10 Ω/sq, which were cleaned and irradiated by
ultraviolet before fabrication. Next, the PEDOT: PSS was spin-coated
onto the treated ITO glass substrates in a glove box, annealed at 120
°C for 20 minutes. Then the solutions of CzPA-F-PD in chlorobenzene
(10 mg/mL) and TFA were prepared according to volume ratios of
CzPA-F-PD:TFA (50/1, v:v), CzPA-F-PD:TFA (5000/1, v:v), and CzPA-F-
PD, respectively. The solutions were then spin-coated to form the
emission layers, followed by the thermal annealing at 50 °C for 10
minutes. After that, bis[2-(diphenylphosphino)phenyl]ether oxide
(DPEPO), 1,3,5-tri(mpyridin-3-ylphenyl)-benzene (TmPyPB), 8-
quinolinolatolithium (Liq) and aluminium (Al) were sequentially
thermal evaporated onto emission layer in a vacuum evaporation
equipment at 5×10-4 Pa. After the fabricating OLED, the luminance
and electroluminescence (EL) spectra and chromaticity coordinates
were measured using PR-735 scan spectrometer. Simultaneously,
the current and voltage were obtained by a Keithley 2400 source. The
current and power efficiencies were calculated from the J-V-L
characteristic curves. The EQE was calculated by combining the J-V-L
characteristic curve and EL spectrum. All measurements were made
at room temperature under ambient conditions after encapsulating
the devices with the UV epoxy.
122.71, 122.29, 112.68, 58.21, 42.91, 29.10, 25.93, 16.82. Elem. anal. Results and discussion
Found: C, 87.88; H, 7.301; N, 7.43. Calcd for CzPA-F-PD: C, 87.10; H,
7.10; N, 5.80. HRMS (MALDI) calcd. for CzPA-F-PD: 964.540; found:
964.250.
Single crystal structure
Single crystals structure of CzPA-F-PD was determined by single-
crystal X-ray diffraction analysis. And, detail crystal structure data
were list in Table S1 (ESI*). Seeing in Fig. 1a, CzPA-F-PD shows rather
smaller twisting angle of 20° between PD unit and fluorene ring,
which makes large π conjugated skeleton; rather bigger twisting
angle of 52° between carbazole unit and phenyl ring, which is due to
strong repulsion between two adjacent hydrogen atoms in carbazole
and phenyl ring. So, it is indicated twisting A-π-D-π-A conformation
of CzPA-F-PD. In addition, it can be found in Fig. 1b that CzPA-F-PD
molecules adopt antiparallel coupling and establish efficient tail-to-
tail interaction with adjacent molecules through C–H……π (2.895 Å)
Molecule and properties
The molecular structure of CzPA-F-PD was confirmed by 1H NMR, 13
C
NMR and mass spectra. The 1H and 13C NMR data were acquired on
Bruker DRX 600 spectrometer at 600 MHz and 151 MHz respectively.
Mass spectrometry was recorded on ultrafleXtreme MALDI TOF/TOF.
Furthermore, elemental analysis was acquired on vario EL cube,
ELEMENTAR.
2 | J. Name., 2012, 00, 1-3
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