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1 Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C. This journal is The Royal Society of Chemistry 215 Electronic Supplementary Information Axial Chiral Aggregation-Induced Emission Luminogens with Aggregation-Annihilated Circular Dichroism Effect Haoke Zhang, a Hongkun Li, c Jia Wang, b Jingzhi Sun, a Anjun Qin* ab and Ben Zhong Tang* abc a ME Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 3127, China. E- mail: qinaj@zju.edu.cn (A.J.Q.). b Guangdong Innovative Research Team, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 5164, 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 & Technology, Clear Water Bay, Kowloon, Hong Kong, China. tangbenz@ust.hk (B.Z.T.). S1

2 TABLE F CNTENTS EXPERIMENTAL SECTIN...S3 Chemicals and materials....s3 General information....s3 Synthesis...S4 Structural characterization...s8 Figure S1. (A) PL spectra of (R)-BINL in THF/water mixtures with different water fractions (f w ). Concentration: 1-5 M. (B) Plot of I/I versus water fraction, I: maximum PL intensity, I : maximum PL intensity at f w = %, λ ex = 3 nm...s8 Figure S2. 1 H NMR spectrum of (R)-6,6'-BTPE-BINA in CDCl 3. The solvent peak is marked with asterisk...s9 Figure S3. 13 C NMR spectrum of (R)-6,6'-BTPE-BINA in CDCl 3. The solvent peak is marked with asterisk....s9 Figure S4. HRMS spectrum of (R)-6,6'-BTPE-BINA....S1 Figure S5. 1 H NMR spectrum of (S)-6,6'-BTPE-BINA in CDCl 3. The solvent peak is marked with asterisk...s1 Figure S6. 13 C NMR spectrum of (S)-6,6'-BTPE-BINA in CDCl 3. The solvent peak is marked with asterisk....s11 Figure S7. HRMS spectrum of (S)-6,6'-BTPE-BINA....S11 Figure S8. 1 H NMR spectrum of (R)-3,3'-BTPE-BINA in CDCl 3. The solvent peaks are marked with asterisks....s12 Figure S9. 13 C NMR spectrum of (R)-3,3'-BTPE-BINA in CDCl 3. The solvent peak is marked with asterisk....s12 Figure S1. HRMS spectrum of (R)-3,3'-BTPE-BINA....S13 Figure S11. 1 H NMR spectrum of (R)-BINL-CH 2 in CDCl 3. The solvent peak is marked with asterisk...s13 Figure S C NMR spectrum of (R)-BINL-CH 2 in CDCl 3. The solvent peak is marked with asterisk...s14 Figure S13. HRMS spectrum of (R)-BINL-CH 2...S14 Results...S15 Figure S14. TGA thermograms of (R)-6,6'-BTPE-BINA, (S)-6,6'-BTPE-BINA and (R)-3,3'- BTPE-BINA recorded under N 2 at a heating rate of 1 o C/min....S15 Figure S15. Absorption spectra of (R)-6,6'-BTPE-BINA, (S)-6,6'-BTPE-BINA and (R)-3,3'- BTPE-BINA in THF. Concentration = 1-5 M....S15 Figure S16. PL spectra of (A) (R)-6,6'-BTPE-BINA, (B) (S)-6,6'-BTPE-BINA and (C) (R)- 3,3'-BTPE-BINA in THF/water mixtures with different f w. Concentration: 1-5 M; λ ex = 33 nm....s16 Figure S17. The plots of quantum yield to (R)-6,6'-BTPE-BINA, (S)-6,6'-BTPE-BINA and (R)-3,3'-BTPE-BINA versus water fraction in the THF/water mixtures. (Reference: Quinine sulfate in.1 N sulfuric acid, Φ F = 56 %)...S16 Figure S18. ptimized molecular structures of (A) (R)-3,3'-BTPE-BINA and B) (S)-6,6'- BTPE-BINA. (The ground-state geometries were optimized through density functional theory (DFT) with a B3LYP hybrid functional at the basis set level of 6-31G (d,p). All the calculations were performed using the Gaussian 3 package.)...s17 S2

3 Figure S19. CD spectra of (R)-6,6'-BTPE-BINA and (S)-6,6'-BTPE-BINA in THF. Concentration: 1-4 M....S17 Figure S2. CD spectra of (A) (R)-6,6'-BTPE-BINA and (B) (S)-6,6'-BTPE-BINA in THF/water mixtures with different f w. Concentration: 1-4 M...S18 Figure S21. Single crystal structure and torsion angles of (R)-3,3'-BTPE-BINA S18 Reference...S18 EXPERIMENTAL SECTIN Chemicals and materials. Dioxane and tetrahydrofuran (THF) were distilled from sodium benzophenone ketyl under nitrogen immediately prior to use. Potassium carbonate (K 2 C 3 ), acetone, dioxane, THF, p-toluene sulfonic acid, and toluene were purchased from Signopharm Chemical Reagent Co., Ltd. (R)-(-)-6,6'-Dibromo-1,1'-binaphthyl-2,2'-diol, (S)-(+)- 6,6'-dibromo-1,1'-binaphthyl-2,2'-diol, (R)-(+)-3,3'-dibromo-1,1'-binaphthyl- 2,2'-diol, (R)-(-)-1,1'-binaphthyl-2,2'-diyl hydrogenphosphate, n-butyllithium, tetrakis (triphenylphosphine) palladium and diiodomethane were obtained from J&K. Diphenylmethane, 4-bromobenzophenone, and bis(pinacolato) diboron were gotten from Energy Chemical. 1-omohexane and potassium Acetate came from Aladdin. 18-Crown-6 were obtained from Shanghai Chemical Reagent. Bis(triphenylphosphine) palladium dichloride was purchased from ABCR GmbH&Co.KG. General information. 1 H and 13 C NMR spectra were measured on uker DMX-5, uker AV 4 or Varian NMR 3 spectrometers in deuterated chloroform (CDCl 3 ) using tetramethylsilane (TMS; δ = ) as internal reference. High-resolution mass spectra (HRMS) were recorded on a GCT premier CAB48 Mass Spectrometer System operating in a MALDI-TF mode. UV-Vis spectra were measured on a Varian CARY 1 Bio UV-visible spectrophotometer. Photoluminescence measurements were recorded on a Shimadzu RF-531PC spectrofluorophotometer. FT-IR spectra were recorded on a uker Vector 22 spectrometer. Particle size was measured on S3

4 ookhaven BI-9 Plus instrument. Thermogravimetric analysis (TGA) measurements were conducted on a TA-Q5 TGA under N 2 atmosphere at a heating rate of 1 o C/min. Circular Dichroism (CD) spectra were recorded on Bio-logic MS-45 spectropolarimeter. Fluorescence quantum yields (Φ F ) were estimated using quinine sulfate in.1 N sulfuric acid (Φ F = 54.6%) as standard. Synthesis 4,4,5,5-Tetramethyl-2-(4-(1,2,2-triphenylvinyl)phenyl)-1,3,2-dioxaborolane (6): This compound was synthesized by our previous published procedures. [1] A white powder was obtained in 85% yield. 1 H NMR (4 MHz, CDCl 3 ), δ (TMS, ppm): 7.66 (d, 2H), (m, 17H), 1.4 (s, 12H). 1). n-buli/thf H p-tsa B B 5 1 2). 2 3 toluene, reflux KAc, Pdcl 2 dppf dioxane, reflux B 4 6 (R)-(-)-6,6'-dibromo-2,2'-bis(hexyloxy)-1,1'-binaphthyl [(R)-1]: 1-omohexane (.76 ml, 5.4 mmol), (R)-(-)-6,6'-dibromo-1,1'-binaphthyl-2,2'-diol (.4 g,.9 mmol), K 2 C 3 (.5 mg, 3.62 mmol) and a catalytic amount of 18-crown-6 (.5 mg,.19 mmol) were added into a 1 ml single-necked flask fitted with an allihn condenser, 5 ml acetone was injected into it to dissolve these materials. After stirring at 7 o C for 24 h, the mixture was extracted with dichloromethane (DCM). The organic layer was washed with deionized water and brine, and dried over anhydrous sodium sulfate. After filtration, the filtrate was evaporated under reduced pressure, and the crude product was purified through a silica gel column chromatograph using petroleum/dichloromethane (2/1, v/v) as eluent. A viscous liquid was obtained in 82% yield (.45 g,.74 mmol). 1 H NMR (3 MHz, CDCl 3 ), δ (TMS, ppm): 8. (s, 2H), 7.83 (d, 2H), 7.41 (d, 2H), 7.27 (d, 2H), 6.98 (d, 2H), (m, 4H), (m, 4H), (m, 12H), (m, 6H). S4

5 H H + 18-crown-6, K 2 C 3 acetone, reflux (R)-7 9 (R)-1 (S)-(+)-6,6'-Dibromo-2,2'-bis(hexyloxy)-1,1'-binaphthyl [(S)-1]: The synthetic procedures are similar with those of (R)-1. A viscous liquid was obtained in 84.4% yield. 1 H NMR (3 MHz, CDCl 3 ), δ (TMS, ppm): 8. (s, 2H), 7.83 (d, 2H), 7.41 (d, 2H), 7.27 (d, 2H), 6.98 (d, 2H), (m, 4H), (m, 4H), (m, 12H), (m, 6H). H H + 18-crown-6, K 2 C 3 acetone, reflux (S)-7 9 (S)-1 (R)-(+)-3,3'-Dibromo-2,2'-bis(hexyloxy)-1,1'-binaphthyl [(R)-11]: The synthetic procedures are similar with those of (R)-1. A white powder was obtained in 86% yield. 1 H NMR (3 MHz, CDCl 3 ), δ (TMS, ppm): 8.24 (s, 2H), 7.8 (d, 2H), (m, 2H), (m, 2H), 7.12 (d, 2H), (m, 2H), (m, 2H), (m, 4H), (m, 4H), (m, 14H). H H + (R) crown-6, K 2 C 3 acetone, reflux (R)-11 (R)-(-)2,2'-bis(hexyloxy)-6,6'-bis(4-(1,2,2-triphenylvinyl)phenyl)-1,1'-binaphthyl [(R)- 6,6'-BTPE-BINA]: (R)-1 (.6 g,.1 mmol), 6 (.9 g,.25 mmol) and a catalytic amount of tetrakis (triphenylphosphine) palladium were added into a two-necked flask fitted with an allihn condenser. The system was degassed and refilled with nitrogen for three times. Then, 5 ml distilled THF was injected, followed with potassium carbonate aqueous solution (1 mg, 15 ml). After stirring at 85 o C for 24 h., the S5

6 mixture was extracted with DCM. The organic layer was washed with deionized water and brine, and dried over anhydrous sodium sulfate. After filtration, the filtrate was evaporated under reduced pressure, and the crude product was purified through a silica gel column chromatograph using petroleum/dichloromethane (5/1, v/v) as eluent. A cyan powder was obtained in 73.2% yield (.8 g,.7 mmol). 1 H NMR (5 MHz, CDCl 3 ), δ (TMS, ppm): 8.1 (s, 2H), 7.93 (d, 2H), (m, 8H), 7.18 (d, 2H), (m, 34H), (m, 4H), 1, (m, 4H), (m, 12H), (m, 6H). 13 C NMR (125MHz, CDCl 3 ), δ (TMS, ppm): 154.7, 143.1, , , 14.97, 14.2, 138.1, , , 131.7, , , , , , 127.6, 127., , , , , , 125.4, 12.43, , 69.73, 31.33, 29.36, 25.33, 22.47, HRMS (MALDI-TF, m/z): [M + ] Calcd for C 84 H 74 2 : (1.%), (9.9%), found: B Pd(PPh 3 ) 4, K 2 C 3 THF, reflux (R)-1 6 (R)-6,6'-BTPE-BINA (S)-(+)-2,2'-Bis(hexyloxy)-6,6'-bis(4-(1,2,2-triphenylvinyl)phenyl)-1,1'-binaphthyl [(S)-6,6'-BTPE-BINA]: The synthesis procedures are similar with those of (R)-6,6'- BTPE-BINA. A cyan powder was obtained in 76% yield. 1 H NMR (5 MHz, CDCl 3 ), δ (TMS, ppm): 8.1 (s, 2H), 7.93 (d, 2H), (m, 8H), 7.18 (d, 2H), (m, 34H), (m, 4H), (m, 4H), (m, 12H), (m, 6H). 13 C NMR (125MHz, CDCl 3 ), δ (TMS, ppm): , 144.8, 144.2, , , 14.89, , 135.7, , 132.3, , , , , 128., , , 126.7, , , , , , , 69.99, 31.6, 29.62, 25.6, 22.74, HRMS (MALDI-TF, m/z): [M + ] Calcd for C 84 H 74 2 : (1.%), (9.9%), found: S6

7 + B Pd(PPh 3 ) 4, K 2 C 3 THF, reflux (S)-1 6 (S)-6,6'-BTPE-BINA (R)-(+)-2,2'-Bis(hexyloxy)-3,3'-bis(4-(1,2,2-triphenylvinyl)phenyl)-1,1'-binaphthyl [(R)-3,3'-BTPE-BINA]: The synthesis procedures are similar with those of (R)-6,6'- BTPE-BINA. A white powder was obtained in 68% yield. 1 H NMR (5 MHz, CDCl 3 ), δ (TMS, ppm): 7.88 (s, 2H), 7.84 (d, 2H), 7.5 (d, 4H), 7.35 (m, 2H), (m, 4H), (m, 34H), 3.33 (m, 2H), 3.6 (m, 2H), (m, 8H), (m, 12H),.48 (m, 2H). 13 C NMR (125MHz, CDCl 3 ), δ (TMS, ppm): , , 144., , , , 141.9, , , , , , 131.4, 13.92, 13.3, 128.9, , 127.9, , , , , , , 72.74, 31.48, 3.5, 25.35, 22.68, HRMS (MALDI-TF, m/z): [M + ] Calcd for C 84 H 74 2 : (1.%), (9.9%), found: B Pd(PPh 3 ) 4, K 2 C 3 THF, reflux (R)-11 6 (R)-3,3'-BTPE-BINA (R)-(-)-1,1'-Binaphthyl-2,2'-methylenedioxy [(R)-BINL-CH 2 ]: (R)-(-)-Binaphthol (.2 g,.7 mmol), CH 2 I 2 (.56 mg, 2.1 mmol), K 2 C 3 (.58 mg, 4.19 mmol), acetone (5 ml) were added into a single-necked flask, then refluxed overnight. Afterward, the mixture was cooled down to room temperature and extracted with S7

8 DCM and water for three times. The organic layer was dried with anhydrous NaS 4, and condensed by a rotatory evaporation under reduced pressure. The crude product was purified through a silica gel column chromatograph using petroleum/dichloromethane (1/1, v/v) as eluent. A white powder was obtained in 71.4% yield (.15 g,.5 mmol). 1 H NMR (5 MHz, CDCl 3 ), δ (TMS, ppm): 7.96 (d, 2H), 7.92 (d, 2H), 7.51 (d, 2H), 7.47 (d, 2H), 7.43 (m, 2H), 7.28 (m, 2H), 5.68 (m, 2H). 13 C NMR (125MHz, CDCl 3 ), δ (TMS, ppm): , , , 13.28, , , 126.7, , 12.88, HRMS (MALDI-TF, m/z): [M + ] Calcd for C 21 H 14 2 : , found: H H CH 2 I 2, K 2 C 3 acetone, reflux (R)-BINL (R)-BINL-CH 2 Structural characterization. PL intensity (au) A water fraction vol% I/I H H B Wavelength (nm) Water fraction (vol%) Figure S1. (A) PL spectra of (R)-BINL in THF/water mixtures with different water fractions (f w ). Concentration: 1-5 M. (B) Plot of I/I versus water fraction, I: maximum PL intensity, I : maximum PL intensity at f w = %, λ ex = 3 nm. S8

9 * Chemical shift (ppm) Figure S2. 1 H NMR spectrum of (R)-6,6'-BTPE-BINA in CDCl 3. The solvent peak is marked with asterisk. * Chemical shift (ppm) Figure S3. 13 C NMR spectrum of (R)-6,6'-BTPE-BINA in CDCl 3. The solvent peak is marked with asterisk. S9

10 lhk-m-6, MW=1115; DCTB tan1411_6 6 (.199) Cn (Cen,4, 5., Ar); Sb (15,1. ); Sm (SG, 2x3.); Cm (2:16) TF LD % m/z Figure S4. HRMS spectrum of (R)-6,6'-BTPE-BINA. * Chemical shift (ppm) Figure S5. 1 H NMR spectrum of (S)-6,6'-BTPE-BINA in CDCl 3. The solvent peak is marked with asterisk. S1

11 * Chemical shift (ppm) Figure S6. 13 C NMR spectrum of (S)-6,6'-BTPE-BINA in CDCl 3. The solvent peak is marked with asterisk. lhk-m-6, MW=1115; DCTB tan1411_6 6 (.199) Cn (Cen,4, 5., Ar); Sb (15,1. ); Sm (SG, 2x3.); Cm (2:16) TF LD % m/z Figure S7. HRMS spectrum of (S)-6,6'-BTPE-BINA. S11

12 * * Chemical shift (ppm) Figure S8. 1 H NMR spectrum of (R)-3,3'-BTPE-BINA in CDCl 3. The solvent peaks are marked with asterisks. * Chemical shift (ppm) Figure S9. 13 C NMR spectrum of (R)-3,3'-BTPE-BINA in CDCl 3. The solvent peak is marked with asterisk. S12

13 tan1411_5 6 (.199) Cn (Cen,4, 5., Ar); Sb (15,1. ); Sm (SG, 2x3.); Cm (1:7) TF LD+ 788 % m/z Figure S1. HRMS spectrum of (R)-3,3'-BTPE-BINA. * Chemical shift (ppm) Figure S11. 1 H NMR spectrum of (R)-BINL-CH 2 in CDCl 3. The solvent peak is marked with asterisk. S13

14 * Chemical shift (ppm) Figure S C NMR spectrum of (R)-BINL-CH 2 in CDCl 3. The solvent peak is marked with asterisk. tan14619_8 6 (.21) Cn (Cen,4, 9., Ar); Sb (15,1. ); Sm (SG, 2x3.); Cm (6) TF LD+ 82. % m/z Figure S13. HRMS spectrum of (R)-BINL-CH 2. S14

15 Results o C 42 o C 425 o C Weight (%) (R)-6,6'-BTPE-BINA (S)-6,6'-BTPE-BINA (R)-3,3'-BTPE-BINA Temperature ( C) Figure S14. TGA thermograms of (R)-6,6'-BTPE-BINA, (S)-6,6'-BTPE-BINA and (R)- 3,3'-BTPE-BINA recorded under N 2 at a heating rate of 1 o C/min. 1.2 L mol cm ) (R)-6,6'-BTPE-BINA (S)-6,6'-BTPE-BINA (R)-3,3'-BTPE-BINA Wavelength (nm) Figure S15. Absorption spectra of (R)-6,6'-BTPE-BINA, (S)-6,6'-BTPE-BINA and (R)- 3,3'-BTPE-BINA in THF. Concentration = 1-5 M. S15

16 PL intensity (au) A water fraction vol 9% 8% 7% 6% 5% 4% 3% 2% 1% % PL intensity (au) B water fraction vol 9% 8% 7% 6% 5% 4% 3% 2% 1% % PL intensity (au) C water fraction vol% Wavelength (nm) Wavelength (nm) Wavelength (nm) Figure S16. PL spectra of (A) (R)-6,6'-BTPE-BINA, (B) (S)-6,6'-BTPE-BINA and (C) (R)-3,3'-BTPE-BINA in THF/water mixtures with different f w. Concentration: 1-5 M; λ ex = 33 nm Quantum yield (%) (R)-6,6'-BTPE-BINA (S)-6,6'-BTPE-BINA (R)-3,3'-BTPE-BINA Water fraction (vol%) Figure S17. The plots of quantum yield to (R)-6,6'-BTPE-BINA, (S)-6,6'-BTPE- BINA and (R)-3,3'-BTPE-BINA versus water fraction in the THF/water mixtures. (Reference: Quinine sulfate in.1 N sulfuric acid, Φ F = 56 %). S16

17 Figure S18. ptimized molecular structures of (A) (R)-3,3'-BTPE-BINA and B) (S)- 6,6'-BTPE-BINA. (The ground-state geometries were optimized through density functional theory (DFT) with a B3LYP hybrid functional at the basis set level of 6-31G (d,p). All the calculations were performed using the Gaussian 3 package.) 3 [ ] (1 5 mdeg ml mmol -1 mm -1 ) (R)-6,6'-BTPE-BINA (S)-6,6'-BTPE-BINA Wavelength (nm) Figure S19. CD spectra of (R)-6,6'-BTPE-BINA and (S)-6,6'-BTPE-BINA in THF. Concentration: 1-4 M. S17

18 [ ] (1 5 mdeg ml mmol -1 mm -1 ) A Water fraction vol % Wavelength (nm) [ ] (1 5 mdeg ml mmol -1 mm -1 ) B Water fraction vol% Wavelength (nm) Figure S2. CD spectra of (A) (R)-6,6'-BTPE-BINA and (B) (S)-6,6'-BTPE-BINA in THF/water mixtures with different f w. Concentration: 1-4 M. Figure S21. Single crystal structure and torsion angles of (R)-3,3'-BTPE-BINA. Reference [1] Y. Liu, C. Deng, L. Tang, A. Qin, R. Hu, J. Sun, B. Z. Tang, J. Am. Chem. Soc ; D. Ding, C. C. Goh, G. Feng, Z. Zhao, J. Liu, R. Liu, N. Tomczak, J. L. Geng, B. Z. Tang, L. G. Ng, B. Liu, Adv. Mater., 213, 25, 683. S18