1,3,5-Triazine Derivatives as New Electron Transport Type Host Materials for Highly Efficient Green Phosphorescent OLEDs. Supporting Information

Transcription

1 1,3,5-Triazine Derivatives as ew Electron Transport Type Host Materials for Highly Efficient Green Phosphorescent OLEDs Hsiao-Fan Chen a, Shang-Jung Yang a, Zhen-Han Tsai b, Wen-Yi Hung* b, Ting-Chih Wang a, Ken-Tsung Wong* a a Department of Chemistry, ational Taiwan University, Taipei 1, Taiwan. Fax ; Tel: ; kenwong@ntu.edu.tw b Institute of Optoelectronic Sciences, ational Taiwan Ocean University, Keelung 22, Fax: ; Tel: ext. 718; wenhung@mail.ntou.edu.tw Supporting Information Synthesis: Tris(2-bromophenyl)triazine. Trifluoromethane sulfonic acid (5. ml, 5.3 mmol) was added to a solution of 3-bromobenzonitrile (5. g, 27.5 mmol) in CH 2 Cl 2 (5 ml). The mixture was stirred for 12 h at room temperature and then quenched through the addition of ahco 3(aq). The aqueous phase was extracted with CH 2 Cl 2, dried (MgSO 4 ), and washed with hexane to afford the title compound (3.1 g, 7%) as a white solid. 1 H MR (CDCl 3, 4 MHz) δ 8.83 (d, J = 2. Hz, 3H), 8.7 (d, J = 8. Hz, 3H), 7.75 (d, J = 8. Hz, 3H), 7.4 (t, J = 8. Hz, 3H); 13 C MR (CDCl 3, 1 MHz) δ 17.5, 137.5, 135., 131.7, 13.2, 127.5, 122.9; HRMS (m/z, ESI + ) calcd for C 21 H Br , found ; calcd for C 21 H Br 81 2 Br , found ; calcd for C 21 H Br 81 Br , found T2T. A mixture of tris(9-bromophenyl)triazine (75 mg, 1.4 mmol), phenylboronic acid (598 mg, 4.9 mmol), Pd(PPh 3 ) 4 (12 mg,.14 mmol), a 2 CO 3(aq) (14 ml, 28 mmol, 2. M), and tri-tert-butylphosphine (5. ml,.28 mmol,.5 M in toluene) in toluene (18 ml) was heated under reflux for 24 h. After cooling to room temperature, the reaction was quenched through the addition of water and then the aqueous phase was extracted with CH 2 Cl 2. The combined organic extracts were dried (MgSO 4 ) and concentrated under rotary evaporation. The resulting solid residue was washed with hexane to give the title compound (752 mg, 99 %) as a white solid. 1 H MR (CDCl 3, 4 MHz) δ 9.3 (s, 3H), 8.78 (d, J = 8. Hz, 3H), 7.8 (d, J = 7.2 Hz, 3H), 7.7 (d, J = 7.2 Hz, H), 7.7 (t, J = 8. Hz, 3H), 7.53 (t, J = 8. Hz, H), 7.44 (d, J = 7.2 Hz, 3H); 13 C MR (CDCl 3, 4 MHz) δ 171.5, 141.5, 14., 13., 131.2, 129., 128.8, S-1

2 127.8, 127., 127.5, 127.2; HRMS (m/z, ESI + ) calcd for C 39 H , found A mixture of tris(9-bromophenyl)triazine (1.58 g, 2.89 mmol), biphenyl-2-boronic acid (2. g, 1.1 mmol), Pd(PPh 3 ) 4 (332 mg,.3 mmol), a 2 CO 3(aq) (2. M, 28.8 ml, 57.8 mmol), and tri-tert-butylphosphine (11.5 ml,. mmol,.5 M in toluene) in toluene ( ml) was heated under reflux for 24 h. After cooling to room temperature, the reaction was quenched through the addition of water and then the aqueous phase was extracted with CH 2 Cl 2. The combined organic extracts were dried (MgSO 4 ) and concentrated under rotary evaporation. The resulting solid residue was washed with hexane to give the title compound (2.17 g, 98%) as a white solid. 1 H MR (CDCl 3, 4 MHz) δ 8.51 (d, J =.2 Hz, 1H), 8.5 (s, 1H), (m, 1H), (m, 3H), (m, 2H), (m, 2H), (m, 3H); 13 C MR (CDCl 3, 4 MHz) δ 171.3, 141.9, 141.3, 14.8, 14.1, 135.9, 134., 13.7, 13.4, 13., 128.1, 127.9, 127.8, 127., 127.2, 12.; HRMS (m/z, ESI + ) calcd for C 57 H , found Trifluoromethanesulfonic acid (1.1 ml, 11.7 mmol) was added to a solution of 9,9 -spirobi[fluorene]-2-carbonitrile (2. g, 5.87 mmol) in CH 2 Cl 2 (3 ml). The mixture was stirred for 12 h at room temperature and then the reaction was quenched through the addition of ahco 3(aq). The mixture was concentrated through rotary evaporation. The resulting suspension was filtered and the solids washed with CH 2 Cl 2 to give the title compound (1.25 g, 3%) as a white solid. 1 H MR (CDCl 3, 4 MHz) δ 8.59 (dd, J = 1.2, 8.2 Hz, 3H), (m, 12H), 7.78 (s, 3H), (m, 9H), 7.14 (t, J =.4 Hz, 3H), 7.8 (t, J = 7. Hz, H),.9 (t, J = 7. Hz, 9H); 13 C MR (CDCl 3, 4 MHz) δ 17.9, 15., 148., 147.9, 14., 141., 14.5, 135., 129.2, 128., 127.8, 127., 124.2, 123.9, 12.5, 12.,.; HRMS (m/z, ESI + ) calcd for C 78 H , found S-2

3 T2T S-3

4 T2T S-4

5 S-5

6 S-

7 S-7

8 S-8

9 ITO/PEDOT/PB (2 nm)/tcta (5 nm)/t2t:ir(ppy) 3 1% (25 nm)/ (5 nm)/lif/al EL Intensity (a.u.) 1. T2T:Ir(PPy) 3.8 T2T Wavelength (nm) Fig. S-1. EL spectra of T2T doped with Ir(PPy) 3 and featuring various s. (a) 1 5 (b) 18 Quantum Efficiency (%) Voltage(V) T2T:Ir(PPy) 3 T2T Current Density (ma/cm 2 ) Power Efficiency (lm/w) Fig. S-2. (a) I V L characteristics and (b) plots of EL efficiency versus brightness for T2T doped with Ir(PPy) 3 and featuring various s. S-9

10 ITO/PEDOT/PB (2 nm)/tcta (5 nm)/:dopant 1% (25 nm)/ (5 nm)/lif/al (a) EL Intensity (a.u.) 1. :(PPy) 2 Ir(acac) Wavelength (nm) (b) EL Intensity (a.u.) 1. :Ir(PPy) Wavelength (nm) Fig. S-3. EL spectra of doped with (a) (PPy) 2 Iracac and (b) Ir(PPy) 3 and featuring various s. (a) 1 5 (b) 18 Quantum Efficiency (%) :(PPy) 2 Ir(acac) Voltage(V) Current Density (ma/cm 2 ) Power Efficiency (lm/w) (c) 1 5 (d) 1 Quantum Efficiency (%) :Ir(PPy) Voltage(V) Current Density (ma/cm 2 ) Power Efficiency (lm/w) Fig. S-4. (a, c) I V L characteristics and (b, d) plots of EL efficiency versus brightness for doped with (PPy) 2 Ir(acac) and Ir(PPy) 3 and featuring various s. S-1

11 ITO/PEDOT/PB (2 nm)/tcta (5 nm)/:dopant 1% (25 nm)/ (5 nm)/lif/al (a) 1. EL Intensity (a.u.) :(PPy) 2 Ir(acac) Wavelength (nm) (b) EL Intensity (a.u.) 1. :Ir(PPy) Wavelength (nm) Fig. S-5. EL spectra of doped with (a) (PPy) 2 Ir(acac) and (b) Ir(PPy) 3 and featuring various s. (a) 1 5 (b) Quantum Efficiency (%) :(PPy) 2 Ir(acac) Voltage(V) Current Density (ma/cm 2 ) Power Efficiency (lm/w) (c) 1 5 (d) Quantum Efficiency (%) :Ir(PPy) Voltage(V) Current Density (ma/cm 2 ) Power Efficiency (lm/w) Fig. S-. (a,c) I V L characteristics and (b, d) plots of EL efficiency versus brightness for doped with (PPy) 2 Ir(acac) and Ir(PPy) 3 and featuring various s. S-11