SUPPORTING INFORMATION

Transcription

1 SUPPORTING INFORMATION RGB Phosphorescent Organic Light-Emitting Diodes by Using Host Materials with Heterocyclic Cores: Effect of Nitrogen Atom Orientations Shi-Jian Su, 1,2 * Chao Cai, 2 and Junji Kido 2 * 1 Institute of Polymer Optoelectronic Materials and Devices, Key Laboratory of Specially Functional Materials of the Ministry of Education, South China University of Technology, Guangzhou 1040, China 2 Department of Organic Device Engineering, Graduate School of Science and Engineering, Yamagata University, Jonan, Yonezawa, Yamagata , Japan mssjsu@scut.edu.cn; kid@yz.yamagata-u.ac.jp Syntheses. 9 was synthesized by cross-coupling between bis(pinacolato)diboron and 8, which was synthesized by Ullmann reaction between 1-bromo-3-iodo-benzene and carbazole. The host materials 1- were synthesized by Suzuki-Miyaura cross-coupling reaction between 9 and aryl halide in the presence of palladium catalyst. 1, 2, and 4 were synthesized with aryl bromide using tetrakis(triphenylphosphine)palladium(0) (Pd(PPh 3 ) 4 ) as the catalyst in the presence of 2M K 2 CO 3 according to the literature procedures.,, and were synthesized with aryl chloride using bis(triphenylphosphine)palladium(ii) chloride (PdCl 2 (PPh 3 ) 2 ) as the catalyst. 3 was synthesized with 2,4-dichloropyridine using tris(dibenzylideneacetone) dipalladium(0) (Pd 2 (dba) 3 ) as the catalyst in the presence of tricyclohexylphosphine (PCy 3 ) and K 3 PO 4. 1,3-bis(3-(carbazol-9-yl)phenyl)benzene (1). 1.0 g, 89%. 1 H NMR (00 MHz, CDCl 3 ): δ (ppm) 8.1 (dd, J=8.0 and 1.0 Hz, 4H),.893 (t, J=2.0 Hz, 1H),.80 (t, J=2.0 Hz, 2H),.8-.3 (m, 2H),.0-. (m, 4H), (m, 3H), (m, 4H), (m, 4H), (m, 4H). 13 C NMR (00 MHz, CDCl 3 ): δ (ppm) , , , 138., 130.0, , , 12.18, , 12.39, , , 123.1, , , EIMS: m/z 1 (M + ) (calcd m/z 0.9). Syntheses of 2,4-bis(3-(carbazol-9-yl)phenyl)pyridine (3). A mixture of 9 (2. g,.20 mmol), 2,4-dichloropyridine (0.444 g, 3.0 mmol), Pd 2 (dba) 3 (0.1 g, 0.18 mmol), PCy 3 (0.121 g, mmol), and K 3 PO 4 (2.1 g, 10.2 mmol) in 1,4-dioxane (100 ml) and water (30 ml) was stirred at 90 for 24 hr under nitrogen atmosphere. After cooling to room temperature, the mixture was poured into water and then extracted with toluene. The combined organic phase was washed with brine and dried over MgSO 4. The subjection of the crude mixture to silica gel chromatography (chloroform/n-hexane = 3/2) afforded 3 (1.44 g, 8%) as white -1-

2 powders. 1 H NMR (00 MHz, CDCl 3 ): δ (ppm) 8. (dd, J=.0 and 1.0 Hz, 1H), 8.2 (t, J=1. Hz, 1H), (m, H),.992 (t, J=1.0 Hz, 1H),.891 (t, J=1. Hz, 1H),.88-. (m, 1H), (m, 2H),.-.3 (m, 1H), (m, 1H),.2 (dd, J=.0 and 1. Hz, 1H), (m, 8H), (m, 4H). 13 C NMR (00 MHz, CDCl 3 ): δ (ppm) 1.28, 10.14, , , 140.9, 140.4, , , , 130.4, , 12.89, 12.49, 12.09, 12.98, , 12.42, , , , , , , , , , EIMS: m/z 2 (calcd m/z 1.). Syntheses of 2,4-bis(3-(carbazol-9-yl)phenyl)pyrimidine (). A mixture of 9 (2. g,.20 mmol), 2,4-dichloropyridine (0.44 g, 3.0 mmol), PdCl 2 (PPh 3 ) 2 (0.10 g, 0.1 mmol), and 2M aqueous potassium carbonate (0 ml) in 1,4-dioxane (120 ml) was stirred at 90 for 24 hr under nitrogen atmosphere. After cooling to room temperature, the mixture was poured into water and then extracted with toluene. The combined organic phase was washed with brine and dried over MgSO 4. The subjection of the crude mixture to silica gel chromatography (chloroform/n-hexane = 3/2) afforded (1. g, 92%) as white powders. 1 H NMR (00 MHz, CDCl 3 ): δ (ppm) (d, J=.0 Hz, 1H), (t, J=1. Hz, 1H), (m, 1H), (t, J=1. Hz, 1H), (m, 1H), (m, 4H), (m, 4H),.3 (d, J=.0 Hz, 1H), (m, 4H), (m, 4H), (m, 4H). 13 C NMR (00 MHz, CDCl 3 ): δ (ppm) , 13.13, , , , 139.2, , , , , , , , 12.33, 12.1, 12.11, , , , 123.0, , , , , , , , EIMS: m/z 3 (calcd m/z 2.). 4,-bis(3-(carbazol-9-yl)phenyl)pyrimidine (). 1.3 g, 9%. 1 H NMR (00 MHz, CDCl 3 ): δ (ppm) (d, J=1. Hz, 1H), 8.38 (t, J=2.0 Hz, 2H), (m, 2H), (m, H),. (t, J=8.0 Hz, 2H), (m, 2H), (m, 8H), (m, 4H). 13 C NMR (00 MHz, CDCl 3 ): δ (ppm) 14.00, , , , 138.1, 130.9, , 12.13, , 12.09, , , 120.1, , EIMS: m/z 3 (calcd m/z 2.). 2,-bis(3-(carbazol-9-yl)phenyl)pyrazine (). 1.0 g, 9%. 1 H NMR (00 MHz, CDCl 3 ): δ (ppm) 9.03 (s, 2H), 8.33 (t, J=2.0 Hz, 2H), (d, J=8.0 Hz, 2H), 8.19 (d, J=8.0 Hz, 4H),.8(t, J=8.0 Hz, 2H),.94 (d, J=8.0 Hz, 2H),.4 (d, J=8.0 Hz, 4H), (m, 4H),.28 (t, J=8.0 Hz, 4H). 13 C NMR (00 MHz, CDCl 3 ): δ (ppm) , 140.3, , , , 130.3, 128., 12.0, , 12.2, , , , EIMS: m/z 3 (calcd m/z 2.). -2-

3 Table S1. Physical properties of 1- Figure S1. Calculated (black bold lines) and experimental (gray bold lines) HOMO and LUMO energy levels of host materials 1- (Top). Calculated (black bold lines) and experimental (gray bold lines) triplet energy levels of host materials 1- (Bottom). Dashed lines are guides to the eye. Also shown cores of the corresponding host materials. Figure S2. Transient photoluminescence decay of vacuum co-deposited films of FIrpic : 1- under excitation by a nitrogen laser (λ = 33 nm, 0 Hz, 800 ps pulses). Also shown their simultaneous photoluminescence spectra as insets. Figure S3. Transient photoluminescence decay of vacuum co-deposited films of Ir(PPy) 3 : 1- under excitation by a nitrogen laser (λ = 33 nm, 0 Hz, 800 ps pulses). Also shown their simultaneous photoluminescence spectra as insets. Figure S4. Transient photoluminescence decay of vacuum co-deposited films of Ir(piq) 3 : 1- under excitation by a nitrogen laser (λ = 33 nm, 0 Hz, 800 ps pulses). Also shown their simultaneous photoluminescence spectra as insets. Figure S. Electroluminescent spectra for (a) ITO / TPDPES:TBPAH (20 nm) / 3DTAPBP (30 nm) / 1-:11 wt% FIrpic (10 nm) / TmPyPBP (40 nm) / LiF (0. nm) / Al (100 nm), (b) ITO / TPDPES:TBPAH (20 nm) / TAPC (30 nm) / 1-: wt% Ir(PPy) 3 (10 nm) / TpPyPhB (0 nm) / LiF (0. nm) / Al (100 nm), and (c) ITO / TPDPES:TBPAH (20 nm) / TAPC (3 nm) / 1- or CBP:4 wt% Ir(piq) 3 (10 nm) / TPyBPZ ( nm) / LiF (0. nm) / Al (100 nm). -3-

4 Table S1. Physical properties of 1- Materials a a b T g T m T d λ abs c d e f λ PL λ phos T 1 HOMO g LUMO h ( ) ( ) ( ) (nm) (nm) (nm) (ev) (ev) (ev) (ev) , 24, 29, 331, , 38, 400 4, 489, , 29, 331, , n.a , 24, 29, 330, , 491, , 243, 29, 331, , , 244, 29, 330, , , 243, 29, 330, , , 29, 331, n.a a Glass transition temperature (T g ) and melting temperature (T m ) obtained from differential scanning calorimetry (DSC) measurement. b Decomposition temperature (T d ) obtained from thermogravimetric analysis (TGA). c UV-vis absorption spectra of vacuum deposited films on quartz substrates at room temperature. d Photoluminescence (PL) spectra of vacuum deposited films on quartz substrates at room temperature. e Phosphorescence spectra of vacuum deposited films on quartz substrates at T = 4.2 K. f Triplet energy level (T 1 ) corresponding to the highest energy peak of phosphorescence spectra. g HOMO energy level determined by atmospheric ultraviolet photoelectron spectroscopy (Rikken Keiki AC-3). h LUMO energy level calculated from HOMO and E g. i Energy band-gap (E g ) from the lowest-energy absorption edge of UV-vis absorption spectra. E g i -4-

5 Figure S1. Calculated (black bold lines) and experimental (gray bold lines) HOMO and LUMO energy levels of host materials 1- (Top). Calculated (black bold lines) and experimental (gray bold lines) triplet energy levels of host materials 1- (Bottom). Dashed lines are guides to the eye. Also shown cores of the corresponding host materials. S

6 Figure S2. Transient photoluminescence decay of vacuum co-deposited films of FIrpic : 1- under excitation by a nitrogen laser (λ = 33 nm, 0 Hz, 800 ps pulses). Also shown their simultaneous photoluminescence spectra as insets. S

7 Figure S3. Transient photoluminescence decay of vacuum co-deposited films of Ir(PPy) 3 : 1- under excitation by a nitrogen laser (λ = 33 nm, 0 Hz, 800 ps pulses). Also shown their simultaneous photoluminescence spectra as insets. S

8 Figure S4. Transient photoluminescence decay of vacuum co-deposited films of Ir(piq) 3 : 1- under excitation by a nitrogen laser (λ = 33 nm, 0 Hz, 800 ps pulses). Also shown their simultaneous photoluminescence spectra as insets. S8

9 a b CBP c Figure S. Electroluminescence spectra for (a) ITO / TPDPES:TBPAH (20 nm) / 3DTAPBP (30 nm) / 1-:11 wt% FIrpic (10 nm) / TmPyPBP (40 nm) / LiF (0. nm) / Al (100 nm), (b) ITO / TPDPES:TBPAH (20 nm) / TAPC (30 nm) / 1-:8 wt% Ir(PPy) 3 (10 nm) / TpPyPhB (0 nm) / LiF (0. nm) / Al (100 nm), and (c) ITO / TPDPES:TBPAH (20 nm) / TAPC (3 nm) / 1- or CBP:4 wt% Ir(piq) 3 (10 nm) / TPyBPZ ( nm) / LiF (0. nm) / Al (100 nm). S9