Electronic Supporting Information

Electronic Supplementary Material (ESI) for Materials Chemistry Frontiers. This journal is the Partner Organisations 2018 Electronic Supporting Information Tetraphenylpyrazine-based luminogens with full-colour emission Lingxiang Pan, a Yuanjing Cai, a Haozhong Wu, a Fan Zhou, a Anjun Qin,* a Zhiming Wang,* a and Ben Zhong Tang* a,b a. State Key Laboratory of Luminescent Materials and Devices, Center for Aggregation-Induced Emission, South China University of Technology, Guangzhou 510640, China. b. Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China Table of contents Experimental Section...S3 Fig. S1. 1 H NMR spectrum of 1 in CDCl 3. The solvent peak is marked with asterisk and the & refers to the H of the unreacted bis(pinacolato)diboron...s5 Fig. S2. 13 C NMR spectrum of 1 in CDCl 3. The solvent peak is marked with asterisk....s5 Fig. S3. 1 H NMR spectrum of DTPP in CDCl 3. The solvent peak is marked with asterisk...s6 Fig. S4. 13 C NMR spectrum of DTPP in CDCl 3. The solvent peak is marked with asterisk)....s6 Fig. S5. 1 H NMR spectrum of DTPP-Ph in CDCl 3. The solvent peak is marked with asterisk....s7 Fig. S6. 13 C NMR spectrum of DTPP-Ph in CDCl 3. The solvent peak is marked with asterisk...s7 Fig. S7. 1 H NMR spectrum of DTPP-BT in CDCl 3. The solvent peak is marked with asterisk....s8 Fig. S8. 13 C NMR spectrum of DTPP-BT in CDCl 3. The solvent peak is marked with asterisk....s8 Fig. S9. 1 H NMR spectrum of DTPP-T in CDCl 3, the solvent peak is marked with asterisk....s9 Fig. S10. 13 C NMR spectrum of DTPP-T in CDCl 3. The solvent peak is marked with asterisk...s9 Fig. S11. 1 H NMR spectrum of DTPP-TO in CDCl 3. The solvent peak is marked with asterisk...s10 Fig. S12. 13 C NMR spectrum of DTPP-TO in CDCl 3. The solvent peak is marked with asterisk...s10 Fig. S13. 1 H NMR spectrum of DTPP-TBTT in CDCl 3. The solvent peak is marked with asterisk....s11 Fig. S14. 13 C NMR spectrum of DTPP-TBTT in CDCl 3. The solvent peak is marked with asterisk....s11 Fig. S15. HRMS spectra of DTPP...S12 Fig. S16. HRMS spectra of DTPP-Ph....S12 Fig. S17. HRMS spectra of DTPP-BT....S12 Fig. S18. HRMS spectra of DTPP-T....S13 Fig. S19. HRMS spectra of DTPP-TO....S13 S1

Fig. S20. HRMS spectra of DTPP-TBTT...S13 Fig. S21. TGA and DSC curves of DTPP, DTPP-Ph, DTPP-BT, DTPP-T, DTPP-TO and DTPP-TBTT...S14 Fig. S22. A) PL spectra of DTPP, DTPP-Ph, DTPP-BT, DTPP-T, DTPP-TO and DTPP-TBTT in THF solutions, concentration: 10 μm, B) Photos of these TPP derivatives in THF solutions, taken under daylight and irradiation of a UV lamp (365 nm)...s14 Fig. S23. PL spectra of A) DTPP-Ph; B) DTPP-T; C ) DTPP-TO in THF/H 2 O mixtures with different water fractions. Concentration: 10 μm....s15 Fig. S24. The time-resolved fluorescence spectra of these TPP derivatives A) in THF solution, concentration: 10μM; B) in solid films...s15 Table S1. The theoretical and experimental energy levels of DTPP, DTPP-Ph, DTPP-BT, DTPP-T, DTPP-TO and DTPP-TBTT...S15 Fig. S25. A) current density-voltage-luminance characteristics, B) dependence of current efficiency, C) external quantum efficiency of the devices I-IV....S16 Fig. S26. Cyclic voltammograms of DTPP-BT, DTPP-TO and DTPP-TBTT, measured in DMF containing 0.1 M tetra-n-butylammonium hexafluorophosphate in reduction process.s16 Reference S16 S2

Experimental Section Materials: All commercially available chemicals were purchased from Energy, TCI, J&K chemistry or Beijing HWRK Chem Co., Ltd., Soochiral Chemical Reagent Co., Ltd. and used directly without further purification. Tetrahydrofuran (THF) and toluene were distilled from sodium benzopheone ketyl under dry nitrogen immediately before use. Instrumentation: All 1 H and 13 C NMR spectra were recorded with a Bruker AV 500 spectrometer in deuterated CDCl 3 using tetramethylsilane (TMS; δ = 0) as internal reference. High resolution mass spectra (HRMS) were tested using a GCT premier CAB048 mass spectrometer operated in MALDI-TOF mode. UV-visible absorption spectra were measured with a SHIMADZU UV-2600 spectrophotometer. PL spectra were recorded on a HORIBA Flioromax-4 spectrofluorometer. Fluorescence quantum yields were measured using a Hamamatsu absolute photoluminescence quantum yield spectrometer C11347 Quantaurus-QY. Thermogravimetric analysis (TGA) analysis was carried out on a TA TGA Q5000 absolute at a heating rate of 20 o C/min under dry nitrogen. Synthesis of compound 1: TPP-Br was prepared according to the literatures. 1-3 TPP-Br (9.24 g, 20 mmol), Bis(pinacolato)diboron (10.16 g, 40 mmol), 1,1'-Bis(diphenylphosphino)ferrocene palladium(ii)dichloride Pd(dppf)Cl 2 (730 mg, 1 mmol), and KOAc (7.85 g, 80 mmol) were added into a 500 ml two neck flask under nitrogen. Then 150 ml 1,4-dioxane was injected into the flask and the reaction was stirred and refluxed 10 h. After removing the solvent under vacuum, the mixture was dissolved in DCM and washed with water three times. The organic phase was dried over Mg 2 SO 4 and concentrated. Finally the crude product was purified by a silicagel column with DCM/hexane (1:10 by volume) as eluent. Oily product was obtained and after creation of vacuum, white solid 1 was obtained in 89.7% yield. 1 H NMR (500 MHz, CDCl 3 ), δ (TMS, ppm): 7.76-7.75(m, 2H), 7.65-7.62 (m, 8H), 7.36-7.29 (m, 9H), 1.35 (s, 12H). 13 C NMR (125 MHz, CDCl 3 ), δ (TMS, ppm): 148.53, 148.47, 148.39, 148.24, 141.17, 138.43, 138.42, 138.35, 134.56, 129.88, 129.15, 128.61, 128.29, 128.23, 128.22, 83.89, 24.89. Synthesis of DTPP: TPP-Br (460 mg, 1.0 mmol), 1 (510 mg, 1.0 mmol), Pd(PPh 3 ) 4 (60 mg, 0.05 mmol) and K 2 CO 3 (280 mg, 2.0 mmol) were added into a 250 ml two neck flask under nitrogen. Then 35 ml THF and 15mL H 2 O were injected and the mixture was refluxed overnight. When the mixture was cooled into the room temperature, a mass of white precipitation can be found in the flask. After filtrating and was washed with ethyl acetate, the crude product was obtained in 78.3% yield. Finally, the crude product was treated with sublimation. S3

1 H NMR (500 MHz, CDCl 3 ), δ (TMS, ppm): 7.74-7.73 (m, 4H), 7.71-7.69 (m, 4H), 7.67-7.64 (m, 8H), 7.60-7.58 (m, 4H), 7.38-7.31 (m, 18H). 13 C NMR (125 MHz, CDCl 3 ), δ (TMS, ppm): 148.43, 148.38, 147.82, 140.52, 138.51, 138.45, 138.43, 137.64, 130.35, 129.89, 128.69, 128.64, 128.34, 128.25, 128.24, 126.81. HRMS (MALDI TOF): m/z 766.3129 [M + ], calcd for C 56 H 38 N 4 766.3096. Synthesis of DTPP-Ph: The reaction and purification methods were similar to that of DTPP. 1 H NMR (500 MHz, CDCl 3 ), δ (TMS, ppm): 7.77-7.74 (m, 4H), 7.73-7.70 (m, 8H), 7.68-7.65 (m, 8H), 7.64-7.61 (m, 4H), 7.38-7.31 (m, 18H). 13 C NMR (125 MHz, CDCl 3 ), δ (TMS, ppm): 148.43, 148.37, 147.86, 140.63, 139.59, 138.52, 138.47, 138.44, 137.50, 130.37, 129.90, 128.69, 128.64, 128.35, 128.26, 128.24, 127.46, 127.42, 127.39, 126.76. HRMS (MALDI TOF): m/z 842.3433 [M + ], calcd for C 62 H 42 N 4 842.3409. Synthesis of (DTPP-BT: The reaction and purification methods were similar to that of DTPP. 1 H NMR (500 MHz, CDCl 3 ), δ (TMS, ppm): 8.00-7.98 (m, 4H), 7.87-7.83 (m, 6H), 7.78-7.74 (m, 4H), 7.71-7.65 (m, 8H), 7.40-7.32 (m, 18H). 13 C NMR (125 MHz, CDCl 3 ), δ (TMS, ppm): 154.04, 148.39, 147.68, 138.49, 138.46, 138.44, 138.42, 137.51, 132.82, 130.15, 129.95, 129.91, 129.06, 128.76, 128.67, 128.40, 128.26, 128.15. HRMS (MALDI TOF): m/z 900.3055 [M + ], calcd for C 62 H 40 N 6 S 900.3035. Synthesis of DTPP-T: The reaction method was similar to that of DTPP, and the crude product was purified by a silica-gel column with DCM/hexane (1:4 by volume) as eluent. Yellow green solid was obtained in 83.1% and then treated with sublimation. 1 H NMR (500 MHz, CDCl 3 ), δ (TMS, ppm): 7.71-7.68 (m, 8H), 7.66-7.64 (m, 8H), 7.58-7.57 (m, 4H), 7.37-7.30 (m, 20H). 13 C NMR (126 MHz, CDCl 3 ), δ (TMS, ppm): 148.36, 148.33, 148.26, 147.53, 143.41, 138.45, 138.40, 138.38, 137.53, 134.34, 130.45, 129.88, 129.86, 128.74, 128.66, 128.65, 128.39, 128.25, 128.24, 125.28, 124.52. HRMS (MALDI TOF): m/z 848.2972 [M + ], calcd for C 60 H 40 N 4 S 848.2974. Synthesis of DTPP-TO: The reaction method was similar to that of DTPP, and the crude product was purified by a silica-gel column with DCM/hexane (1:4 by volume) as eluent. Yellow solid was obtained in 79.6% and then treated with sublimation. 1 H NMR (500 MHz, CDCl 3 ), δ (TMS, ppm): 7.79-7.77 (m, 4H), 7.76-7.73 (m, 4H), 7.69-7.64 (m, 12H), 7.41-7.31 (m, 18H), 7.05 (s, 2H). 13 C NMR (125 MHz, CDCl 3 ), δ (TMS, ppm): 148.71, 148.47, 148.45, 146.86, 141.45, 140.39, 138.24, 138.23, 138.13, 130.73, 129.90, 129.88, 129.86, 128.96, 128.78, 128.76, 128.52, 128.30, 128.27, 127.13, 126.15, 120.79. HRMS (MALDI TOF): m/z 880.2852 [M + ], calcd for C 60 H 40 N 4 O 2 S 880.2872. S4

Synthesis of DTPP-TBTT: The reaction and purification methods were similar to that of DTPP. 1 H NMR (500 MHz, CDCl 3 ), δ (TMS, ppm): 8.14-8.13 (d, 2H), 7.92 (s, 2H), 7.73-7.70 (m, 8H), 7.69-7.65 (m, 12H), 7.47-7.46 (d, 2H), 7.39-7.31 (m, 18H). 13 C NMR (125 MHz, CDCl 3 ), δ (TMS, ppm): 152.56, 148.40, 148.38, 148.32, 147.53, 145.05, 139.02, 138.46, 138.42, 138.39, 137.79, 134.24, 130.49, 129.88, 128.76, 128.69, 128.67, 128.40, 128.27, 128.24, 125.78, 125.49, 125.40, 124.50. HRMS (MALDI TOF): m/z 1064.2794 [M + ], calcd for C 70 H 44 N 6 S 3 1064.2790. Fig. S1. 1 H NMR spectrum of 1 in CDCl 3. The solvent peak is marked with asterisk and the & refers to the H of the unreacted bis(pinacolato)diboron. Fig. S2. 13 C NMR spectrum of 1 in CDCl 3. The solvent peak is marked with asterisk. S5

Fig. S3. 1 H NMR spectrum of DTPP in CDCl 3. The solvent peak is marked with asterisk. Fig. S4. 13 C NMR spectrum of DTPP in CDCl 3. The solvent peak is marked with asterisk. S6

Fig. S5. 1 H NMR spectrum of DTPP-Ph in CDCl 3. The solvent peak is marked with asterisk. Fig. S6. 13 C NMR spectrum of DTPP-Ph in CDCl 3. The solvent peak is marked with asterisk. S7

Fig. S7. 1 H NMR spectrum of DTPP-BT in CDCl 3. The solvent peak is marked with asterisk. Fig. S8. 13 C NMR spectrum of DTPP-BT in CDCl 3. The solvent peak is marked with asterisk. S8

Fig. S9. 1 H NMR spectrum of DTPP-T in CDCl 3. The solvent peak is marked with asterisk. Fig. S10. 13 C NMR spectrum of DTPP-T in CDCl 3. The solvent peak is marked with asterisk. S9

Fig. S11. 1 H NMR spectrum of DTPP-TO in CDCl 3. The solvent peak is marked with asterisk. Fig. S12. 13 C NMR spectrum of DTPP-TO in CDCl 3. The solvent peak is marked with asterisk. S10

Fig. S13. 1 H NMR spectrum of DTPP-TBTT in CDCl 3. The solvent peak is marked with asterisk. Fig. S14. 13 C NMR spectrum of DTPP-TBTT in CDCl 3. The solvent peak is marked with asterisk. S11

cm-tpp-tpp; MW=766; DCTB tan161206_1 9 (0.298) Cn (Cen,4, 90.00, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (7:11) 100 766.3129 TOF LD+ 515 767.3225 % 768.3257 769.3212 0 688.4005 583.3282 682.4392 690.3714 751.4435 580 600 620 640 660 680 700 720 740 760 780 800 820 840 860 880 900 920 940 770.2601 832.4948 m/z Fig. S15. HRMS spectra of DTPP. cm-plx-tpp-ph-tpp, MW=842; DCTB tan160505_5 13 (0.433) Cn (Cen,4, 90.00, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (8:15) 100 842.3433 TOF LD+ 619 843.3459 % 844.3479 845.3549 865.3381 918.3772 841.4191 867.3485 920.3847 751.4491 0 575 600 625 650 675 700 725 750 775 800 825 850 875 900 925 950 975 1000 1025 1050 1075 m/z Fig. S16. HRMS spectra of DTPP-Ph. zz-pan-9; MW=900; DCTB tan160126_9 4 (0.133) Cn (Cen,4, 90.00, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (4:8) 100 900.3055 TOF LD+ 423 901.3096 % 902.3085 903.3062 904.3380 0 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 Fig. S17 HRMS spectra of DTPP-BT m/z S12

cm-tpp-t-tpp; MW=849; DCTB tan161206_3 6 (0.201) Cn (Cen,4, 90.00, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (2:8) 100 848.2972 TOF LD+ 1.29e3 849.2993 % 850.2939 851.3014 930.2991 852.3060 932.2991 688.3730 853.2426 0 m/z 575 600 625 650 675 700 725 750 775 800 825 850 875 900 925 950 975 1000 1025 1050 1075 1100 Fig. S18. HRMS spectra of DTPP-T. cm-tpp-to-tpp; MW=881; DCTB tan161206_4 5 (0.164) Cn (Cen,4, 90.00, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (2:12) 100 880.2852 TOF LD+ 4.50e3 881.2374 % 882.2272 883.2651 0 1067.4568 1131.4191 884.2730 832.2872 848.2700 1068.4446 902.3278 1133.4128 1069.4744 1130.3901 850.2998 903.3401 688.3596 904.3499 1134.3884 645.2156 583.2827 751.3936 816.3037 600 650 700 750 800 850 900 950 1000 1050 1100 1150 m/z Fig. S19. HRMS spectra of DTPP-TO. cm-tpp-tbt-tpp; MW=1065; DCTB tan161206_5 9 (0.298) Cn (Cen,4, 90.00, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (3:9) 100 1064.2794 TOF LD+ 1.22e3 1065.2808 1066.2815 % 1067.3009 993.2228 994.2236 1068.3336 1363.2930 995.2303 980.0929 1068.7181 1365.3007 783.1388 996.2323 1291.2330 688.3735 0 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250 1300 1350 1400 1450 m/z Fig. S20. HRMS spectra of DTPP-TBTT. S13

100 A B DTPP-TBTT 80 Weight (%) 60 40 DTPP DTPP-Ph DTPP-BT DTPP-T DTPP-TO DTPP-TBTT Enthalpy (a.u.) DTPP-Ph DTPP-BT 20 0 0 150 300 450 600 750 900 Temperature ( o C) 50 100 150 200 250 Temperature ( o C) DTPP-T Fig. S21. TGA and DSC curves of DTPP, DTPP-Ph, DTPP-BT, DTPP-T, DTPP-TO and DTPP-TBTT. Normalized PL Intensity (au) DTPP DTPP-Ph DTPP-BT DTPP-T DTPP-TO DTPP-TBTT 350 450 550 650 750 850 Wavelength (nm) Fig. S22. A) PL spectra of DTPP, DTPP-Ph, DTPP-BT, DTPP-T, DTPP-TO and DTPP-TBTT in THF solutions, concentration: 10 μm, B) Photos of these TPP derivatives in THF solutions, taken under daylight and irradiation of a UV lamp (365 nm). S14

PL Intensity (au) A Water fraction (Vol %) 90 80 70 60 50 40 30 20 10 00 PL Intensity (au) B Water fraction (Vol %) 00 10 20 30 40 50 60 70 80 90 PL Intensity (au) C Water fraction (Vol %) 00 10 20 30 40 50 60 70 80 90 370 420 470 520 570 Wavelength (nm) 400 450 500 550 600 Wavelength (nm) 450 500 550 600 650 700 Wavelength (nm) Fig. S23. PL spectra of A) DTPP-Ph, B) DTPP-T, and C ) DTPP-TO in THF/H 2 O mixtures with different water fractions. Concentration: 10 μm A B Intensity (au) 10 4 DTPP DTPP-Ph DTPP-BT 10 3 DTPP-T DTPP-TO DTPP-TBTT 10 2 10 1 Intensity (au) 10 4 DTPP DTPP-Ph DTPP-BT 10 3 DTPP-T DTPP-TO DTPP-TBTT 10 2 10 1 10 0 0 20 40 60 80 100 Time (ns) 10 0 0 20 40 60 80 100 Time (ns) Fig. S24 The time-resolved fluorescence spectra of these TPP derivatives A) in THF solution, concentration: 10μM; B) in solid films. Table S1 The theoretical and experimental energy levels of DTPP, DTPP-Ph, DTPP-BT, DTPP-T, DTPP-TO and DTPP-TBTT. Compound Theoretical energy level a [ev] Experimental energy level b [ev] HOMO LUMO E g HOMO c LUMO d E e g DTPP -5.44-1.79 3.65-5.74-2.61 3.13 DTPP-Ph -5.44-1.76 3.68-5.81-2.68 3.13 DTPP-BT -5.44-2.47 2.97-5.78-3.08 2.70 DTPP-T -5.23-1.92 3.31-5.55-2.73 2.82 DTPP-TO -5.50-2.61 2.89-5.85-3.35 2.50 DTPP-TBTT -5.03-2.70 2.33-5.33-3.26 2.07 a. calculated by DFT/B3LYP/6-31G(d). b. Determined by cyclic voltammetry. c. E HOMO = - (E onset + 4.4) ev. d. E HOMO = E LUMO + E g. e. E g = 1240/ edge. S15

Current Efficiency (cd/a) 10 1 10 0 C I II III IV Luminance (cd/m 2 ) 10 4 10 3 10 2 10 1 B I II III IV 700 600 500 400 300 200 100 Current Density ma/cm 2 External Quantum Efficiency (%) 1 C I II III IV 10 0 10 1 10 2 10 3 10 4 Luminance (cd/m 2 ) 10 0 0 0 3 6 9 12 15 Voltage (V) 10 0 10 1 10 2 10 3 10 4 Luminance (cd/m 2 ) Fig. S25. A) current density-voltage-luminance characteristics, B) dependence of current efficiency, C) external quantum efficiency of the devices I-IV. DTPP-TO DTPP-TBTT DTPP-BT -1.6-1.2-0.8-0.4 Voltage (V) Fig. S26. Cyclic voltammograms of DTPP-BT, DTPP-TO and DTPP-TBTT, measured in DMF containing 0.1 M tetra-n-butylammonium hexafluorophosphate in reduction process, scan rate: 100 mv s -1. Reference 1. L. Pan, W. Luo, M. Chen, J. Liu, L. Xu, R. Hu, Z. Zhao, A. Qin, and B. Z. Tang, Chin. J. Org. Chem., 2016, 36, 1316-1324. 2. M. Chen, H. Nie, B. Song, L. Li, J. Z. Sun, A. Qin and B. Z. Tang, J. Mater. Chem. C, 2016, 4, 2901-2908. 3. P. Karastatiris, J. A. Mikroyannidis, I. K. Spiliopoulos, A. P. Kulkarni and S. A. Jenekhe, Macromolecules, 2004, 37, 7867-7878. S16