Diagnostic Absolute Configuration Determination of. Tetraphenylethene Core-Based Chiral Aggregation-

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1 Supporting information for Diagnostic Absolute Configuration Determination of Tetraphenylethene Core-Based Chiral Aggregation- Induced Emission Compounds: Particular Fingerprint Bands in Comprehensive Chiroptical Spectroscopy Dan Li, Rongrong Hu,*, Dong Guo, Qiguang Zang, Jianhui Li, Yuekui Wang, Yan-Song Zheng, Ben Zhong Tang, *,, Hui Zhang*, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen , P. R. China State Key Laboratory of Luminescent Materials and Device, South China University of Technology, Guangzhou , P. R. China Key Laboratory of Chemical Biology and Molecular Engineering of the Education Ministry, Institute of Molecular Science, Shanxi University, Taiyuan, Shanxi , P. R. China Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan , P. R. China. Department of Chemistry, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, P. R. China. *Corresponding authors: S1

2 Block diagram of CD spectrometer Figure S1. The block diagram of the optical-electronic layout of ECD and VCD spectrometer. The UV-Vis/FT-IR radiation passes through an optical filter, then linearly polarised, continuously passing through the photo-elastic modulator (PEM), ultimately reaches to the sample cell and absorbed by the sample. Significant improvements in artifact suppression and baseline stability have been achieved through a dual-pem (PEM1 and PEM2) into the Dual-PEM FTIR-VCD spectrometer. Although there is only one PEM (PEM1) in the ECD spectrometer so far, double PEM is the tendency to substantially improve signal-to-noise (S/N) ratios. Figure S2. Comparison of powder X-ray diffraction patterns of TPE, BETPE and TETPE. S2

3 Item Table S1 Crystallographic and structural refinement parameters Value Crystal form TPE BETPE 1 TETPE TETPE 2 Empirical formula C 26 H 20 C 30 H 20 C 34 H 20 C 34 H 20 Formula weight T/K 99.98(13) 173(2) (2) Crystal system Monoclinic Orthorhombic Monoclinic Monoclinic Space group P2 1 P I2 C2 Wavelength/nm a/å (7) (10) (3) (3) b/å (4) (2) 8.834(3) (18) c/å (7) (2) (4) (2) α/ o β/ o (8) (5) (3) γ/ o Volume/Å (11) (5) (6) (4) Z Calculated density/(g cm 3 ) F(000) Final R indices [I > 2σ (I)] R = wr 2 = R = wr 2 = R = wr 2 = R = wr 2 = Flack parameter 0.0(2) CCDC No We tried to determine the AC of TPE through the single-crystal XRD using very intensive X-ray for more than 20 times but the result is not very good. We summarized our result and some of the reported singlecrystal XRD measurements in Table S1, but all these results fail to provide definitively reliable information to determine the AC. Figure S3. Molecular structure of the compound 6 and the crystal structures of M-6 and P-6. S3

4 Table S2 Excitation parameters and involved transitions for the main excited states of TPE No. a Sym b λ(nm) c f d R e (DBM) f µ g (D) h m i (BM) j θ( ) k Transition Assignation l B π π * B π π * B π π * B π π * B π π * B π π * B π π * B π π * B π π * B π π * a Number of the excited states. b Symmetries of excited states (Sym). c Excitation wavelengths(λ) of the excited states. d Oscillator strengths(f). e Rotational (R) strengths. f DBM = Debye-Bohr-Magneton. g Electric dipole transition moments(µ). h D = Debye (1D = C m). i Magnetic dipole transition moments(m). j BM = Bohr-Magneton. k The angle (θ) between the electric (µ) and magnetic (m) dipole transition moments. l Dominant orbital transitions involved in the excitations. S4

5 Table S3 Excitation parameters and involved transitions for the main excited states of BETPE No. a Sym b λ(nm) c f d R e (DBM) f µ g (D) h m i (BM) j θ( ) k Transition Assignation l B π π * A π π * A π π * B π π * A π π * A π π * B π π * A π π * A π π * B π π * A π π * A π π * a Number of the excited states. b Symmetries of excited states (Sym). c Excitation wavelengths (λ) of the excited states. d Oscillator strengths(f). e Rotational (R) strengths. f DBM = Debye-Bohr-Magneton. g Electric dipole transition moments(µ). h D = Debye(1D = C m). i Magnetic dipole transition moments(m). j BM = Bohr-Magneton. k The angle (θ) between the electric (µ) and magnetic (m) dipole transition moments. l Dominant orbital transitions involved in the excitations. S5

6 Table S4 Excitation parameters and involved transitions for the main excited states of TETPE No. a Sym b λ(nm) c f d R e (DBM) f µ g (D) h m i (BM) j θ( ) k Transition Assignation l B π π * B π π * B π π * B π π * B π π * B π π * B π π * B π π * B π π * B π π * B π π * B π π * B π π * a Number of the excited states. b Symmetries of excited states (Sym). c Excitation wavelengths (λ) of the excited states. d Oscillator strengths(f). e Rotational (R) strengths. f DBM = Debye-Bohr-Magneton. g Electric dipole transition moments(µ). h D = Debye (1D = C m). I Magnetic dipole transition moments(m). j BM = Bohr-Magneton. k The angle (θ) between the electric (µ) and magnetic (m) dipole transition moments. l Dominant orbital transitions involved in the excitations. S6

7 Optimized Structure TPE 0 1 C C H C H C H C H C H C C C H C H C H C H C H C C C H C H C H C H C H C C H S7

8 C H C H C H C H BETPE 0 1 C C C C H C C H C C C H C H C H C H C H C H C C C H C H C H C S8

9 H C C H C H C C H C H C H C H C H C H TETPE 0 1 C C C H C H C C H C H C C H C C H C H C S9

10 C H C H C C H C C C H C H C C H C H C C H C C H C H C C H C H C C H S10

11 REFERENCES (1) Hu, R.; Lam, J. W. Y.; Liu, J.; Sung, H. H. Y.; Williams, I. D.; Yue, Z.; Wong, K. S.; Yuen, M. M. F.; Tang, B. Z. Hyperbranched Conjugated Poly(Tetraphenylethene): Synthesis, Aggregation-Induced Emission, Fluorescent Photopatterning, Optical Limiting and Explosive Detection. Polym. Chem. 2012, 3, (2) Tanaka, K.; Hiratsuka, T.; Kojima, Y.; Osano, Y. T. Synthesis, Structure and Chiral Inclusion Crystallization of Tetrakis(4-Ethynylphenyl)Ethylene Derivatives. J. Chem. Res. 2002, 2002, S11