1 Controlled emission colors and singlet triplet. 2 energy gaps of dihydrophenazine-based thermally. 3 activated delayed fluorescence emitters

Transcription

1 Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C. This journal is The Royal Society of Chemistry Controlled emission colors and singlet triplet energy gaps of dihydrophenazine-based thermally activated delayed fluorescence emitters 5 Jiyoung Lee, a Katsuyuki Shizu, b,c iroyuki Tanaka, b 6 ajime akanotani, b,d Takuma Yasuda, a,b,e ironori Kaji c 7 and Chihaya Adachi* b,e 8 9 a Department of Automotive Science, Graduate School of Integrated Frontier Sciences, 10 Kyushu University, 7 Motooka, ishi, Fukuoka , Japan 11 b Center for Organic Photonics and Electronics Research (OPERA), Kyushu University, 1 7 Motooka, ishi, Fukuoka , Japan 1 c Institute for Chemical Research, Kyoto University, Uji, Kyoto , Japan 1 d Innovative Organic Device Laboratory, Institute of Systems, Information Technologies 15 and ano-technologies (ISIT), 7, Motooka, ishi, Fukuoka , Japan. 16 e International Institute for Carbon eutral Energy Research (WPI-ICER), Kyushu 17 University, 7 Motooka, ishi, Fukuoka , Japan. 1

2 1 1. Preparation of 5,10-dihydrophenazine S1 a S O EtO O To a mixture of phenazine (5.00 g, 7.7 mmol) in ethanol (16 ml) was added, with 5 stirring, a solution of sodium dithionate (8. g, 77 mmol) in water (50 ml). The 6 mixture was stirred and heated under reflux for h. A white precipitate was collected 7 and washed with water. The collected solids were dried under reduced pressure to afford 8 5,10-dihydrophenazine (5.0 g, 7.5 mmol). This material was used in the next step 9 without further purification [MS] 1 MALDI-MS m/z Calcd for C 1 10 : 18; found: 18.

3 1. Preparation of 5,10-bis(-(1-phenyl-1-benzoimidazol--yl)phenyl)-5,10- dihydrophenazine (DPZ-BI) Br K CO, Pd(OAc), P(t-Bu) Toluene 5 6 To a mixture of -(-bromophenyl)-1-phenyl-1-benzimidazole (. g, 1.1 mmol) 7 that was synthesized by a reported method, S dihydrophenazine (1.00 g, 5.9 mmol) and 8 potassium carbonate (.55 g,.9 mmol) in toluene (0 ml) was added, with stirring, a 9 solution of palladium(ii) acetate (7.1 mg, 0. mmol) and tri-tert-butylphosphine 10 (.8 mg, 1.1 mmol) in toluene (0 ml). The mixture was stirred and heated under 11 reflux for 1 day. The cooled mixture was filtered and washed with toluene, ethanol, 1 water, and ethanol sequentially. The resulting yellow solid was dried under reduced 1 pressure to afford DPZ-BI (.8 g, 5. mmol). The yield was over 97.0%. The 1 compound was further purified by sublimation under reduced pressure for OLED 15 fabrication [MR] 18 1 MR (CDCl, 00 Mz) = 7.8(d, 8), 7.6(m, 10), 7.9(d, ), 7.5(m, 8), (d, ) 0 [MS] 1 MALDI-MS m/z Calcd for C 50 6 : 719; found: 719. [Elemental analysis] Calcd for C 50 6 : C, 8.5;,.77;, 11.69; found: C, 8.6;,.7;, [Thermal properties] 5 T c : 197 C; T m : 6 C; T d : 8 C (temperature at 5% weight loss from TGA).

4 1. Preparation of, -(phenazine-5,10-diyl)dibenzonitrile (DPZ-B) Br K CO, Pd(OAc), P(t-Bu) Toluene C 5 To a mixture of -bromobenzonitrile (.0 g, 1.1 mmol), dihydrophenazine (1.00 g, mmol) and potassium carbonate (.55 g,.9 mmol) in toluene (0 ml) was added, 7 with stirring, a solution of palladium(ii) acetate (7.1 mg, 0. mmol) and tri-tert- 8 butylphosphine (.8 mg, 1.1 mmol) in toluene (0 ml). The mixture was stirred and 9 heated under reflux for 1 day. The cooled mixture was partitioned between chloroform 10 and water. The organic layer was separated, and the aqueous layer was extracted with 11 large amounts of chloroform. The combined organic layers were washed with brine, 1 dried over MgSO, and concentrated in vacuo. exane (0 ml) was added and an 1 orange insoluble solid was separated by filtration. Then, the collected solid was washed 1 with a mixture of hexane and chloroform (:1) and dried under reduced pressure to give 15 DPZ-B (1.98 g, 5.16 mmol). The yield was over 9%. DPZ-B was further 16 purified by sublimation under reduced pressure for OLED fabrication [MR] 19 1 MR (CDCl, 500 Mz) = 5.91(m, ), 6.5(m, ), 7.50(d,, J = 8. z), (d,, J = 8. z) 1 [MS] MALDI-MS m/z Calcd for C 6 16 : 8; found: 8. [Elemental analysis] Calcd for C 6 16 : C, 81.;,.0;, 1.57; found: C, 81.7;,.11;, [Thermal properties] 6 T d : 51 C (temperature at 5% weight loss from TGA) C C

5 1. Preparation of 5,10-bis(-(benzothiazol--yl)phenyl)-5,10-dihydrophenazine (DPZ-BTZ) Br K CO, Pd(OAc), P(t-Bu) Toluene S 5 6 To a mixture of -(-bromophenyl)benzothiazole (.51 g, 1.1 mmol), 7 dihydrophenazine (1.00 g, 5.9 mmol) and potassium carbonate (.55 g,.9 mmol) in 8 toluene (0 ml) was added, with stirring, a solution of palladium(ii) acetate (7.1 mg, 9 0. mmol) and tri-tert-butylphosphine (.8 mg, 1.1 mmol) in toluene (0 ml). The 10 mixture was stirred and heated under reflux for 1 day. The cooled mixture was filtered 11 and washed with toluene, ethanol, water, and ethanol sequentially. The resulting reddish 1 orange solid was dried under reduced pressure to afford DPZ-BTZ (.77 g,.61 1 mmol). The yield was over 8%. DPZ-BTZ was further purified by sublimation 1 under reduced pressure for OLED fabrication [MR] 17 1 MR (CDCl, 00 Mz) = 5.78(m, ), 6.(m, ), 7.(t, ), 7.5(t, ), (d, ), 7.95(d, ), 8.11(d, ), 8.5(d, ) 19 [MS] 0 MALDI-MS m/z Calcd for C 8 S : 601; found: [Elemental analysis] Calcd for C 8 S : C, 75.97;,.0;, 9.; found: C, 75.91;,.10;, 9.8. [Thermal properties] T c : 5 C; T m : 87 C; T d : 61 C (temperature at 5% weight loss from TGA) S S 5

6 1 5. Preparation of 5,10-bis(-(,6-diphenyl-1,,5-triazin--yl)phenyl)-5,10- dihydrophenazine (DPZ-TRZ) Br K CO, Pd(OAc), P(t-Bu) Toluene 5 6 To a mixture of -(-bromophenyl)-,6-diphenyl-1,,5-triazine (.69 g, 1.1 mmol) that 7 was synthesized by a reported method, S dihydrophenazine (1.00 g, 5.9 mmol) and 8 potassium carbonate (.55 g,.9 mmol) in toluene (0 ml) was added, with stirring, a 9 solution of palladium(ii) acetate (7.1 mg, 0. mmol) and tri-tert-butylphosphine 10 (.8 mg, 1.1 mmol) in toluene (0 ml). The mixture was stirred and heated under 11 reflux for 1 day. The cooled mixture was partitioned between chloroform and water. 1 The organic layer was separated, and the aqueous layer was extracted with large 1 amounts of chloroform. The combined organic layers were washed with brine, dried 1 over MgSO, and concentrated in vacuo. exane (0 ml) was added and the resulting 15 red insoluble solid was separated by filtration. Then, the collected solid was washed 16 with a mixture of hexane and chloroform (:1) and dried under reduced pressure to 17 afford DPZ-TRZ (.7 g,.67 mmol). The yield was over 85%. DPZ-TRZ was 18 further purified by sublimation under reduced pressure for OLED fabrication [MR] 1 1 MR (CDCl, 500 Mz) = 7.6(m, ), 8.8(m, 1) [MS] MALDI-MS m/z Calcd for C : 797; found: 797 [Elemental analysis] 5 Calcd for C : C, 81.9;,.55;, 1.06; found: C, 81.5;,.9;, [Thermal properties] 7 T d : 96 C (temperature at 5% weight loss from TGA) 6

7 1 6. Photoluminescence characteristics in toluene solution Supplementary Table S1. Photoluminescence characteristics of DPZ-BI, DPZ- B, DPZ-BTZ, and DPZ-TRZ (Fig. 1) in toluene solution. τ p and τ d are lifetimes 5 of prompt and delayed components, respectively. The delayed components were not 6 observed in air. 7 Compound In air After nitrogen bubbling PLQY (%) τ p (ns) τ d (μs) PLQY (%) τ p (ns) τ d (μs) DPZ-BI DPZ-B DPZ-BTZ DPZ-TRZ

8 1 7. Calculated and experimental absorption and emission wavelengths Supplementary Table S: Absorption (λ ab ) and emission wavelengths (λ em ) for DPZ- BI, DPZ-B, DPZ-BTZ, and DPZ-TRZ were computed using time- 5 dependent density functional theory (TD-DFT) at the CAM-BLYP/cc-pVDZ level of 6 theory. Solvent effects were taken into account by means of the polarizable continuum 7 model. 8 Compound λ ab (nm) λ em (nm) Calc. Exp. Calc. Exp. DPZ-BI DPZ-B DPZ-BTZ DPZ-TRZ Calculated S 1 -T 1 energy gaps 1 1 Supplementary Table S: S 1 -T 1 energy gaps (ΔE ST ) of DPZ-BI, DPZ-B, 1 DPZ-BTZ, and DPZ-TRZ calculated using the TD-CAM-BLYP/cc- 15 pvdz//cam-blyp/cc-pvdz method Compound ΔE ST (ev) DPZ-BI 0.8 DPZ-B 0.60 DPZ-BTZ 0.5 DPZ-TRZ 0. 8

9 1 9. Photoluminescence characteristics of a 6 wt% DPZ-B:m-CBP film. 5 Supplementary Fig. S1: (a) Transient PL decay curves for a 6 wt% DPZ-B:m- 6 CBP film measured at temperatures of 50 to 00 K. (b) Fluorescence and 7 phosphorescence spectra of the doped film measured at K. Green and black lines show 8 fluorescence and phosphorescence spectra, respectively. 9

10 1 10. Photoluminescence characteristics of a 6 wt% DPZ-BTZ:m-CBP film. 5 Supplementary Fig. S: (a) Transient PL decay curves for a 6 wt% DPZ-BTZ:m- 6 CBP film measured at temperatures of 50 to 00 K. (b) Fluorescence and 7 phosphorescence spectra of the doped film measured at K. Yellow and black lines 8 show fluorescence and phosphorescence spectra, respectively. 10

11 1 11. Transient photoluminescence decays for a 6 wt% DPZ-TRZ:m-CBP film. 5 Supplementary Fig. S: Transient PL decay curves for a 6 wt% DPZ-TRZ:m-CBP 6 film measured at temperatures of 50 to 00 K. 11

12 1 References S1. X.-Q. Zhu, Z. Dai, A. Yu, S. Wu, J.-P. Cheng, J. Phys. Chem. B, 11, (008). 5 S. M. Debeaux, M. W. Thesen, D. Schneidenbach,. opf, S. Janietz,. Krüger, A. 6 Wedel, W. Kowalsky,.-. Johannes, Adv. Funct. Mater., 0, (010). 7 S.. Tanaka, K. Shizu,. Miyazaki, C. Adachi, Chem. Commun. 8, (01). 1