Electronic Supplementary Material (ESI) for Chemical Science. This journal is The Royal Society of Chemistry 2015 Electronic Supplementary Information Tetraphenylpyrazine-Based AIEgens: Facile Preparation and Tunable Light Emission Ming Chen, a Lingzhi Li, a Han Nie, b Jiaqi Tong, a Lulin Yan, d Bin Xu, d Jing Zhi Sun, a Wenjing Tian, d Zujin Zhao, b Anjun Qin,* ab and Ben Zhong Tang* abc a MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China. E-mail: qinaj@zju.edu.cn b Guangdong Innovative Research Team, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China c Department of Chemistry, Institute for Advanced Study, Institute of Molecular Functional Materials, and State Key Laboratory of Molecular Neuroscience, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong China. E-mail: tangbenz@ust.uk d State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun 130012, China. S1
Table of contents Experimental Section S5 Figure S1. 1 H NMR spectrum of TPP in CDCl 3. The solvent peak is marked with asterisk. S10 Figure S2. 13 C NMR spectrum of TPP in CDCl 3. S11 Figure S3. 1 H NMR spectrum of TPP-4M in CDCl 3. The solvent peak is marked with asterisk. S11 Figure S4. 13 C NMR spectrum of TPP-4M in CDCl 3. The solvent peak is marked with asterisk. S12 Figure S5. 1 H NMR spectrum of 8 in DMSO-d 6. S12 Figure S6. 13 C NMR spectrum of 8 in CDCl 3. The solvent peak is marked with asterisk. S13 Figure S7. 1 H NMR spectrum of 9 in CDCl 3. The solvent peak is marked with asterisk. S13 Figure S8. 13 C NMR spectrum of 9 in CDCl 3. The solvent peak is marked with asterisk. S14 Figure S9. 1 H NMR spectrum of 10 in CDCl 3. The solvent peak is marked with asterisk. S14 Figure S10. 13 C NMR spectrum of 10 in CDCl 3. The solvent peak is marked with asterisk. S15 Figure S11. 1 H NMR spectrum of 11 in CDCl 3. The solvent peak is marked with asterisk. S15 Figure S12. 13 C NMR spectrum of 11 in CDCl 3. The solvent peak is marked with asterisk. S16 Figure S13. 1 H NMR spectrum of 12 in CDCl 3. The solvent peak is marked with asterisk. S16 Figure S14. 13 C NMR spectrum of 12 in CDCl 3. S17 Figure S15. 1 H NMR spectrum of 13 in CDCl 3. The solvent peak is marked with S2
asterisk. S17 Figure S16. 13 C NMR spectrum of 13 in CDCl 3. The solvent peak is marked with asterisk. S18 Figure S17. 1 H NMR spectrum of TPP-2P in CDCl 3. The solvent peak is marked with asterisk. S18 Figure S18. 13 C NMR spectrum of TPP-2P in CDCl 3. S19 Figure S19. 1 H NMR spectrum of TPP-2PM in CDCl 3. The solvent peak is marked with asterisk. S19 Figure S20. 13 C NMR spectrum of TPP-2PM in CDCl 3. The solvent peaks are marked with asterisk. S20 Figure S21. 1 H NMR spectrum of TPP-2MP in CDCl 3. The solvent peak is marked with asterisk. S20 Figure S22. 13 C NMR spectrum of TPP-2MP in CDCl 3. The solvent peak is marked with asterisk. S21 Figure S23. 1 H NMR spectrum of TPP-2MPM in CDCl 3. The solvent peak is marked with asterisk. S21 Figure S24. 13 C NMR spectrum of TPP-2MPM in CDCl 3. The solvent peak is marked with asterisk. S22 Figure S25. HRMS spectra of TPP. S22 Figure S26. HRMS spectra of TPP-4M. S23 Figure S27. HRMS spectra of TPP-2P. S23 Figure S28. HRMS spectra of TPP-2PM. S24 Figure S29. HRMS spectra of TPP-2MP. S24 Figure S30. HRMS spectra of TPP-2MPM. S25 Figure S31. TGA curves of AIEgens under nitrogen at a heating rate of 10 o C/min. S25 S3
Figure S32. TGA curves of TPP and its derivatives under nitrogen at a heating rate of 10 o C/min. S26 Figure S33.PL spectra of pristine and treated TPP in THF/water mixtures with ~90% water fractions. Concentration: 10-5 M. ex : 338 nm. The acid and base are 0.1 ml HCl or NaOH aqueous solution (1M), respectively. S26 Figure S34. 1 H NMR spectra of DSA before (A) and after (B) irradiation by a UV light of 365 nm for 2 h in CDCl 3. S27 Figure S35. 1 H NMR spectra of TPP before (A) and after (B) irradiation by a UV light of 365 nm with a power of 1.10 mw/cm 2 for 2 h in CDCl 3. The solvent peaks are marked with asterisk. S27 Figure S36. PL spectra of TPP-2P in THF/water mixtures with different water fraction. Concentration: 10-5 M, λ ex = 347 nm. S28 Figure S37. PL spectra of TPP-2PM in THF/water mixtures with different water fraction. Concentration: 10-5 M, λ ex = 352 nm. S28 Figure S38. PL spectra of TPP-2MPM in THF/water mixtures with different water fraction. Concentration: 10-5 M, λ ex = 362 nm. S29 Figure S39. PL spectra of TPP-2MP in THF/water mixtures with different water fraction. Concentration: 10-5 M, λ ex = 359 nm. S29 Figure S40. PL spectra of TPP-4M in THF/water mixtures with different water fraction. 10-5 M, λ ex = 360 nm. S30 Figure S41. Molecular structures and torsion angles of TPP. S30 Figure S42. Molecular structures and torsion angles of TPP-4M. S31 Figure S43. Molecular structures and torsion angles of TPP-2P. S31 Figure S44. Molecular structures and torsion angles of TPP-2PM. S31 Figure S45. Normalized PL spectra of TPP derivatives in THF. Concentration: 10 M. S32 Scheme S1. Synthetic route to TPP-2PCN. S32 Figure S46. 1 H NMR spectrum of TPP-2PCN in CDCl 3. S33 Figure S47. PL spectra of TPP-2PCN in THF/water mixtures with different water fraction. Concentration: 10-5 M, λ ex = 347 nm. S33 S4
Table S1. Optical and thermal properties of TPP and its derivatives. S34 Table S2. Particle sizes of TPP-based AIEgens in THF/water mixtures. S34 References S34 Experimental Section Materials: All commercially available chemicals were purchased from Alfa Aesar, J&K chemistry or Sinopharm Chemical Reagent Co., Ltd and used directly without further purification. Tetrahydrofuran (THF) and 1,4-dioxane 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 AVANCE III 500 spectrometer using CDCl 3 or DMSO-d 6 as solvent. 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 Varian CARY 100 Biospectrophotometer. PL spectra were recorded on a RF-5301 PC spectrofluorometer. PL quantum efficiency ( F ) was measured with standard quinine sulfate in 0.1N H 2 SO 4 ( F = 0.54) or anthracene in ethanol ( F = 0.27). The absolute F values were recorded with a Hamamatsu Quantaurus-QY C11347 spectrometer. Thermogravimetric analysis (TGA) was carried out with a PerkinElmer TGA 7 at a heating rate of 10 o C/min under dry nitrogen. Single crystal X-ray diffraction was carried out on a Gemini A Ultra diffractometer at 293K. Synthesis of tetraphenylpyrazine (TPP): Rout A: The compound was synthesized accord to the literature with slight modification. 1 Into a 50 ml round bottom flask was added 2.12 g (10 mmol) of benzoin, 1.45 ml (15 mmol) of acetic anhydride, 2.32 g S5
(30 mmol) of ammonium acetate and 10 ml acetic acid. After refluxing for 3.5 h, the mixture was cooled down to room temperature and then filtered. Route B 2 : Into a 50 ml round bottom flask was added 212 mg (1 mmol) of 1,2- diphenylethane-1,2-diamine, 210 mg (1 mmol) of benzyl and 2 ml of acetic acid. The mixture was allowed to reflux for 4 h. Afterwards, the mixture was cooled down to room temperature and filtered. The crude products were purified with recrystallization in acetic acid three times. White crystal, yield: 33.9% (route A); 46.9% (route B). 1 H NMR (500 MHz CDCl 3 ): (TMS, ppm) 7.65 (m, 8H), 7.33 (m, 12H). 13 C NMR (125 MHz, CDCl 3 ): (TMS, ppm) 148.5, 138.5, 129.9, 128.7, 128.3. HRMS (MALDI-TOF): m/z 384.1664 ([M] + ), calcd for C 28 H 20 N 2 384.1626). Synthesis of TPP derivative (TPP-4M): The synthetic method was similar to that of TPP. White crystal, yield: 20 %. 1 H NMR (500 MHz CDCl 3 ): (TMS, ppm) 7.61 (d, 8H), 6.86 (d, 8H), 3.82 (s, 12H). 13 C NMR (125 MHz, CDCl 3 ): (TMS, ppm) 159.9, 146.8, 131.1, 113.7, 55.3. HRMS (MALDI-TOF): m/z 504.2039 ([M] + ), calcd for C 32 H 28 N 2 O 4 : 504.2049). Synthesis of 1-(4-bromophenyl)-2-phenylethanone (8): The product was prepared according to the literature procedure. 3 Into a 250 ml round bottom flask was added 10 g (50 mmol) of 4-bromophenyl boronic acid (5), 1.32 g (2.5 mmol) of Ni(dppe)Cl 2 and 5.1 g (37.5 mmol) of ZnCl 2 under nitrogen. Then, 75 ml of 1,4-dioxane, 2.9 ml (25 mmol) of phenylacetonitrile (6) and 0.45 ml (25 mmol) of water was injected into the flask and the reaction was allowed to stir at 80 o C for 8 h. Afterward, the S6
mixture was filtered and the residue was washed with THF three times. Then the filtrate was concentrated and further dissolved in DCM, and washed with water to remove residual 1,4-dioxane. The collected organic phase was condensed and purified by a silica-gel column with ethyl acetate/hexane (1:20 by volume) as eluent. White solid 8 was obtained in 74.4% yield. 1 H NMR (500 MHz, DMSO-d 6 ): (TMS, ppm) 7.99 (d, 2H), 7.76 (d, 2H), 7.26 (m, 5H), 4.39 (s, 2H). 13 C NMR (125 MHz, CDCl 3 ): (TMS, ppm) 196.8, 135.5, 134.4, 132.2, 130.4, 129.6, 129.0, 128.6, 127.3, 45.8. Synthesis of 1-(4-bromophenyl)-2-(4-methoxyphenyl)ethanone (9): The synthetic method was similar to that of 8. White solid, yield: 67.0 %. 1 H NMR (500 MHz, CDCl 3 ): (TMS, ppm) 7.87 (d, 2H), 7.60 (d, 2H), 7.17 (d, 2H), 6.87 (d, 2H), 4.19 (s, 2H), 3.78 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ): (TMS, ppm) 196.9, 158.6, 135.1, 131.9, 130.4, 130.2, 128.3, 126.1, 114.2, 55.3, 44.7. Synthesis of 1-(4-bromophenyl)-2-hydroxy-2-phenylethanone (10): The product was prepared according to the literature procedure. 3 Into a 250mL round bottom flask was added 6 g (22 mmol) of 9, 150 ml of dimethyl sulfoxide and 7.5 ml of water. After complete dissolution, 20.5 g (52.8mmol) of PHI(OH)OTs was added into the mixtures in two times. The reaction was kept at room temperature for 24 h. After reaction, the mixture was poured into the water and extracted with ethyl acetate. The collected organic phase was first washed with a large amount of water, and then condensed and purified by a silica-gel column with ethyl acetate/hexane (1:10 by volume) as eluent. White solid 10 was obtained in 35.4% yield. 1 H NMR (500 MHz, CDCl 3 ): (TMS, ppm) 7.78 (d, 2H), 7.54 (d, 2H), 7.32 (m, 5H), 5.89 (s, 1H) 4.47 (s, S7
1H). 13 C NMR (125 MHz, CDCl 3 ): (TMS, ppm) 198.3, 138.9, 132.3, 130.8, 129.5, 129.0, 128.0, 76.6. Synthesis of 1-(4-bromophenyl)-2-hydroxy-2-(4-methoxyphenyl)ethanone (11): The synthetic method was similar to that of 10. Yellow viscous liquid, yield: 34.4 %. 1 H NMR (500 MHz, CDCl 3 ): (TMS, ppm) 7.77 (d, 2H), 7.54 (d, 2H), 7.23 (d, 2H), 6.86 (d, 2H), 5.85 (s, 1H), 4.41 (s, 1H), 3.76 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ): (TMS, ppm) 198.1, 159.9, 132.3, 132.0, 130.8, 130.6, 129.1, 114.7, 75.8, 55.3. Synthesis of 12: The synthetic method was similar to that of TPP with method A. White solid, yield: 18.6 %. 1 H NMR (500 MHz, CDCl 3 ): (TMS, ppm) 7.61 (m, 4H), 7.50 (m, 4H), 7.46 (m, 4H), 7.36 (m, 6H). 13 C NMR (125 MHz, CDCl 3 ): (TMS, ppm) 148.6, 148.4, 147.4, 147.2, 138.0, 137.2, 131.5, 131.4, 129.8, 129.0, 128.5, 123.3. Synthesis of 13: The synthetic method was similar to that of TPP with method A. White solid, yield: 23.5 %. 1 H NMR (500 MHz, CDCl 3 ): (TMS, ppm) 7.56 (m, 8H), 7.45 (d, 4H), 6.87 (d, 4H), 3.83 (s, 6H). 13 C NMR (125 MHz, CDCl 3 ): (TMS, ppm) 160.3, 148.0, 147.5, 146.8, 146.1, 137.6, 131.5, 131.4, 131.3, 131.2, 131.1, 130.3, 123.0, 113.9, 55.3. Synthesis of TPP-2P: Into a 250 ml round bottom flask was added 120 mg (0.22 mmol) of 12, 66 mg (0.54 mmol) of benzoboric acid, 12.8 mg (0.011 mmol) of Pd(PPh 3 ) 4, 10 ml of THF and 1.38 g of K 2 CO 3 (dissolved in 5 ml of water) under nitrogen. The mixture was allowed for stir at 80 o C for12 h. After cooled down to room temperature, the mixture was diluted with dichloromethane and washed with S8
NH 4 Cl aqueous solution. The collected organic phase was condensed and purified by a silica-gel column with ethyl acetate/hexane (1:50 by volume) as eluent. White solid, yield: 58.9 %. 1 H NMR (500 MHz, CDCl 3 ): (TMS, ppm) 7.74 (m, 8H), 7.64 (d, 4H), 7.59 (d, 4H), 7.45 (t, 4H), 7.37 (m, 8H). 13 C NMR (125 MHz, CDCl 3 ): (TMS, ppm) 148.6, 148.5, 148.2, 148.1, 141.5, 140.7, 138.7, 137.6, 130.6, 130.2, 129.1, 129.0, 128.6, 127.8, 127.3, 127.2. HRMS (MALDI-TOF): m/z 536.2248 ([M] + ), calcd for C 40 H 28 N 2 536.2252 ). Synthesis of TPP-2PM: The synthetic method was similar to that of TPP-2P. White solid, yield: 68.2 %. 1 H NMR (500 MHz, CDCl 3 ): (TMS, ppm) 7.72 (m, 8H), 7.57 (d, 4H), 7.52 (d, 4H), 7.35 (m, 6H), 6.97 (d, 4H), 3.85 (s, 6H). 13 C NMR (125 MHz, CDCl 3 ): (TMS, ppm) 159.6, 148.5, 148.4, 148.2, 148.0, 141.2, 138.8, 137.0, 133.2, 130.5, 130.1, 128.9, 128.6, 128.3, 126.7, 114.5, 55.6. HRMS (MALDI-TOF): m/z 596.2462 ([M] + ), calcd for C 42 H 32 N 2 O 2 596.2464 ). Synthesis of TPP-2MP: The synthetic method was similar to that of TPP-2P. White solid, yield: 79.3 %. 1 H NMR (500 MHz, CDCl 3 ): (TMS, ppm) 7.77 (d, 4H), 7.66 (m, 8H), 7.60 (d, 4H), 7.45 (t, 4H), 7.36 (t, 2H), 6.89 (d, 4H), 3.83 (6H). 13 C NMR (125 MHz, CDCl 3 ): (TMS, ppm) 160.1, 147.7, 147.4, 147.2, 146.9, 141.1, 140.6, 137.9, 131.3, 130.9, 130.2, 128.8, 127.5, 127.1, 127.0, 113.8, 55.3. HRMS (MALDI- TOF): m/z 596.2457 ([M] +, calcd for C 42 H 32 N 2 O 2 596.2464 ). Synthesis of TPP-2MPM: The synthetic method was similar to that of TPP-2P. White solid, yield: 62.9 %. 1 H NMR (500 MHz, CDCl 3 ): (TMS, ppm) 7.74 (d, 4H), 7.65 (d, 4H), 7.58 (d, 4H), 7.53 (d, 4H), 6.99 (d, 4H), 6.88 (d, 4H), 3.86 (s, 6H), 3.83 S9
(s, 6H). 13 C NMR (125 MHz, CDCl 3 ): (TMS, ppm) 160.1, 159.4, 147.5, 147.3, 147.2, 146.9, 140.6, 137.2, 133.0, 131.3, 131.0, 130.2, 128.1, 126.4, 114.3, 113.7, 55.4, 55.3. HRMS (MALDI-TOF): m/z 656.2658 ([M] +, calcd for C 44 H 36 N 2 O 4 656.2675). Synthesis of TPP-2PCN: Into a 100 ml round bottom flask was added 60 mg (0.11 mmol) of 12, 48 mg (0.33 mmol) of 15 and 12.8 mg (0.011 mmol) of Pd(PPh 3 ) 4, 10 ml of toluene, 5 ml of EtOH and 1.38 g K 2 CO 3 (dissolved in 5 ml of water) under nitrogen. The mixture was reacted at 110 o C for 6 h. Afterwards, solvent was removed by reduced pressure distillation and the residue was washed with dichloromethane and water. The collected organic phases were concentrated and the product was purified by a silica-gel column with dichloromethane/hexane (4:5 by volume) as eluent. White solid TPP-2PCN was obtained in 80% yield. 1 H NMR (300 MHz, CDCl 3 ): δ (TMS, ppm) 7.72 (m, 16H), 7.59 (m, 4H), 7.39 (m, 6H). S10
* 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 Figure S1. 1 H NMR spectrum of TPP in CDCl 3. The solvent peak is marked with asterisk. 150 145 140 135 130 125 Figure S2. 13 C NMR spectrum of TPP in CDCl 3. S11
* 8.0 7.6 7.2 6.8 4.4 4.0 3.6 Figure S3. 1 H NMR spectrum of TPP-4M in CDCl 3. The solvent peak is marked with asterisk. * 160 140 120 100 80 60 40 Figure S4. 13 C NMR spectrum of TPP-4M in CDCl 3. The solvent peak is marked with asterisk. S12
8.2 8.0 7.8 7.6 7.4 7.2 7.0 6.8 4.6 4.4 4.2 Figure S5. 1 H NMR spectrum of 8 in DMSO-d 6. * 200 180 160 140 120 100 80 60 40 Figure S6. 13 C NMR spectrum of 8 in CDCl 3. The solvent peak is marked with asterisk. S13
* 8.0 7.8 7.6 7.4 7.2 7.0 6.8 4.4 4.2 4.0 3.8 3.6 Figure S7. 1 H NMR spectrum of 9 in CDCl 3. The solvent peak is marked with * asterisk. * 200 180 160 140 120 100 80 60 40 Figure S8. 13 C NMR spectrum of 9 in CDCl 3. The solvent peak is marked with asterisk. S14
* 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 Figure S9. 1 H NMR spectrum of 10 in CDCl 3. The solvent peak is marked with asterisk. * 200 180 160 140 120 100 80 60 Figure S10. 13 C NMR spectrum of 10 in CDCl 3. The solvent peak is marked with asterisk. S15
* 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 Figure S11. 1 H NMR spectrum of 11 in CDCl 3. The solvent peak is marked with asterisk. * 200 180 160 140 120 100 80 60 Figure S12. 13 C NMR spectrum of 11 in CDCl 3. The solvent peak is marked with asterisk. S16
* 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 Figure S13. 1 H NMR spectrum of 12 in CDCl 3. The solvent peak is marked with asterisk. 150 145 140 135 130 125 120 Figure S14. 13 C NMR spectrum of 12 in CDCl 3. S17
* 7.8 7.6 7.4 7.2 7.0 6.8 4.0 3.8 3.6 Figure S15. 1 H NMR spectrum of 13 in CDCl 3. The solvent peak is marked with asterisk. * 170 150 130 110 90 70 50 Figure S16. 13 C NMR spectrum of 13 in CDCl 3. The solvent peak is marked with asterisk. S18
* 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 Figure S17. 1 H NMR spectrum of TPP-2P in CDCl 3. The solvent peak is marked with asterisk. 150 145 140 135 130 125 Figure S18. 13 C NMR spectrum of TPP-2P in CDCl 3. S19
* 8.0 7.8 7.6 7.4 7.2 7.0 6.8 4.0 3.8 3.6 Figure S19. 1 H NMR spectrum of TPP-2PM in CDCl 3. The solvent peak is marked with asterisk. * * 160 140 120 100 80 60 Figure S20. 13 C NMR spectrum of TPP-2PM in CDCl 3. The solvent peaks are marked with asterisk. S20
* 8.0 7.8 7.6 7.4 7.2 7.0 6.8 4.0 3.8 3.6 Figure S21. 1 H NMR spectrum of TPP-2MP in CDCl 3. The solvent peak is marked with asterisk. * 170 150 130 110 90 70 50 Figure S22. 13 C NMR spectrum of TPP-2MP in CDCl 3. The solvent peak is marked with asterisk. S21
* 8.0 7.8 7.6 7.4 7.2 7.0 6.8 4.0 3.8 3.6 Figure S23. 1 H NMR spectrum of TPP-2MPM in CDCl 3. The solvent peak is marked with asterisk. * 170 150 130 110 90 70 50 Figure S24. 13 C NMR spectrum of TPP-2MPM in CDCl 3. The solvent peak is marked with asterisk. S22
jm-cm-1, MW=384, DCTB tan140916_2 5 (0.164) Cn (Med,4, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (5:10) 100 384.1664 TOF LD+ 276 385.1680 % 499.2924 386.1733 250.1346 501.2997 313.1343 268.1467 498.3054 292.2078 383.3415 387.2034 502.3026 523.2638 332.2406 195.1092 217.1284 177.0981 235.0850 338.3351 428.2608 452.3124 550.4122 0 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 m/z Figure S25. HRMS spectra of TPP. jm-cm-2, MW=504; DCTB tan131218_9 8 (0.266) Cn (Cen,4, 50.00, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (3:9) 100 504.2039 TOF LD+ 349 % 505.2052 506.2044 503.2646 517.2238 690.1360 759.0143 824.1888 0 m/z 100 125 150 175 200 225 250 275 300 325 350 375 400 425 450 475 500 525 550 575 600 625 650 675 700 725 750 775 800 825 850 Figure S26. HRMS spectra of TPP-4M. S23
jm-cm-3, MW=536, DCTB tan140916_1 6 (0.200) Cn (Med,4, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (2:11) 100 536.2248 TOF LD+ 1.02e3 537.2271 % 538.2288 539.2241 460.2014 500.2831 612.2503 273.1319 372.2424 565.2219 735.4781 773.2750 786.3575 799.4638 0 150 175 200 225 250 275 300 325 350 375 400 425 450 475 500 525 550 575 600 625 650 675 700 725 750 775 800 825 m/z Figure S27. HRMS spectra of TPP-2P. jm-cm-4, MW=596; DCTB tan131218_10 1 (0.033) Cn (Cen,4, 50.00, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (1:8) 100 596.2462 TOF LD+ 1.24e3 597.2512 % 598.2601 599.2921 595.3273 672.2864 324.0687 509.1875 600.3418 909.3407 0 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 m/z Figure S28. HRMS spectra of TPP-2PM. S24
jm-cm-5, MW=596; DCTB tan131218_11 13 (0.432) Cn (Cen,4, 50.00, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (9:14) 100 596.2457 TOF LD+ 404 597.2473 % 598.2550 599.2866 520.2112 250.1451 273.1383 500.2915 563.2240 0 m/z 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 Figure S29. HRMS spectra of TPP-2MP. jm-cm-6, MW=656; DCTB tan131218_12 5 (0.164) Cn (Cen,4, 50.00, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (1:8) 100 656.2658 TOF LD+ 437 657.2696 % 658.2644 659.2511 655.3252 425.9233 864.5511 776.3079 917.8329 0 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 m/z Figure S30. HRMS spectra of TPP-2MPM. S25
100 Weight (%) 80 60 40 TPP TPE HPS DSA 20 0 0 200 400 600 Temperature ( o C) Figure S31. TGA curves of AIEgens under nitrogen at a heating rate of 10 o C/min. 100 80 Weight (%) 60 40 20 TPP TPP-2P TPP-2PM TPP-2MPM TPP-2MP TPP-4M 0 0 200 400 600 800 Temperature ( o C) Figure S32. TGA curves of TPP and its derivatives under nitrogen at a heating rate of 10 o C/min. S26
pristine treated with acid treated with base PL intensity (au) 360 420 480 540 Wavelength (nm) Figure S33.PL spectra of pristine and treated TPP in THF/water mixtures with ~90% water fractions. Concentration: 10-5 M. ex : 338 nm. The acid and base are 0.1 ml HCl or NaOH aqueous solution (1M), respectively. A a * b b a B * 8.4 8.2 8.0 7.8 7.6 7.4 7.2 7.0 6.8 Figure S34. 1 H NMR spectra of DSA before (A) and after (B) irradiation by a UV light of 365 nm for 2 h in CDCl 3. S27
A * B * 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 Figure S35. 1 H NMR spectra of TPP before (A) and after (B) irradiation by a UV light of 365 nm with a power of 1.10 mw/cm 2 for 2 h in CDCl 3. The solvent peaks are marked with asterisk. PL intensity (au) Water fraction vol % 90 80 70 60 50 40 30 20 10 0 380 430 480 530 580 Wavelength (nm) Figure S36. PL spectra of TPP-2P in THF/water mixtures with different water fraction. Concentration: 10-5 M, λ ex = 347 nm. S28
PL intensity (au) Water fraction vol % 90 80 70 60 50 40 30 20 10 0 390 440 490 540 590 Wavelength (nm) Figure S37. PL spectra of TPP-2PM in THF/water mixtures with different water fraction. Concentration: 10-5 M, λ ex = 352 nm. PL intensity (au) Water fraction vol % 90 80 70 60 50 40 30 20 10 0 380 430 480 530 580 Wavelength (nm) Figure S38. PL spectra of TPP-2MPM in THF/water mixtures with different water fraction. Concentration: 10-5 M, λ ex = 362 nm. S29
PL intensity (au) Water fraction vol % 90 80 70 60 50 40 30 20 10 0 370 420 470 520 570 Wavelength (nm) Figure S39. PL spectra of TPP-2MP in THF/water mixtures with different water fraction. Concentration: 10-5 M, λ ex = 359 nm. PL intensity (au) Water fraction vol % 90 80 70 60 50 40 30 20 10 0 370 410 450 490 Wavelength (nm) Figure S40. PL spectra of TPP-4M in THF/water mixtures with different water fraction. 10-5 M, λ ex = 360 nm. S30
Figure S41. Molecular structures and torsion angles of TPP. Figure S42. Molecular structures and torsion angles of TPP-4M. S31
Figure S43. Molecular structures and torsion angles of TPP-2P. Figure S44. Molecular structures and torsion angles of TPP-2PM. S32
Normalized PL intensity 1.0 0.8 0.6 0.4 0.2 TPP TPP-2P TPP-2PM TPP-2MPM TPP-2MP TPP-4M 0.0 350 400 450 500 550 600 Wavelength (nm) Figure S45. Normalized PL spectra of TPP derivatives in THF. Concentration: 10 M. Br N N HO + B CN HO Pd(PPh 3 ) 4, K 2 CO 3 toluene/etoh/h 2 O Br 12 15 NC N N CN TPP-2PCN yield: 80% Scheme S1. Synthetic route to TPP-2PCN. S33
NC N N CN 7.9 7.8 7.7 7.6 7.5 7.4 7.3 Figure S46. 1 H NMR spectrum of TPP-2PCN in CDCl 3. PL intensity (au) Water fraction vol % 90 80 70 60 50 40 30 20 10 0 380 430 480 530 580 Wavelength (nm) Figure S47. PL spectra of TPP-2PCN in THF/water mixtures with different water fraction. Concentration: 10-5 M, λ ex = 347 nm. Table S1. Optical and thermal properties of TPP and its derivatives. S34
λ ab /nm λ em,s /nm λ em,f /nm Ф F,sol /% Ф F,agg /% Ф Fe /% T d / o C TPP 338 390 390 0.53 a 5.70 a,c 8.3 275 TPP-2P 347 423 442 1.00 b 8.50 b,c 9.2 359 TPP-2PM 352 438 453 1.20 b 11.1 b,d 18.1 410 TPP-2MPM 362 460 460 1.30 b 16.3 b,d 14.6 359 TPP-2MP 359 455 440 0.84 b 12.5 b,c 18.5 374 TPP-4M 360 433 428 0.42 a 17.3 a,d 30.7 337 a Measured using anthracene in ethanol as standard ( F = 0.27). b Measured using quinine sulfate in 0.1N H 2 SO 4 as standard ( f = 0.54). c Aggregates formed in THF/water mixtures with f w of 90%. d Aggregates formed in THF/water mixtures with f w of 80%. e Measured using Hamamatsu Quantaurus-QY C11347 spectrometer. Table S2. Particle sizes of TPP-based AIEgens in THF/water mixtures. a f w (%) b TPP TPP-2P TPP-2PM TPP-2MPM TPP-2MP TPP-4M 0 0 0 0 0 0 0 80 140 72 64 84 207 287 90 220 32 31 40 37 139 a Measured by DLS, the unit for the particle size is nm. b f w = water fraction. References 1. D. Davidson, M. Weiss and M. Jelling, J. Org. Chem. 1937, 2, 328-334. 2. U. Ghosh, D. Ganessunker, V. J. Sattigeri, K. E. Carlson, D. J. Mortensen, B. S. Katzenellenbogen and J. A. Katzenellenbogen, Bioorg. Med. Chem., 2003, 11, 629. 3. Y. Wong, K. Parthasarathy and C. Cheng, Org. Lett. 2010, 12, 1736-1739. 4. Y. Xie and Z. Chen, Synth. Commun. 2002, 32, 1875-1879. S35