SERS and NMR Studies of Typical Aggregation-induced. Emission Molecules

Transcription

1 Supplemental information SERS and NMR Studies of Typical Aggregation-induced Emission Molecules Cheng Fang, Yujun Xie, Martin R. Johnston, Yinlan Ruan, Ben Zhong Tang 5, *, Qian Peng, *, Youhong Tang 6, * Global Centre for Environmental Remediation, University of Newcastle, New South Wales, 8, Australia Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Science (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 9, China Centre for NanoScale Science and Technology, School of Chemical and Physical Sciences, Flinders University, South Australia 5, Australia Institute of Photonics and Advanced Sensing, School of Physical Science, The University of Adelaide, Adelaide 55, Australia 5 Department of Chemistry, The Hong Kong University of Science and Technology, Hong Kong, China 6 Centre for NanoScale Science and Technology, School of Computer Science, Engineering and Mathematics, Flinders University, South Australia 5, Australia

2 . Computational Details The molecular geometry optimizations and Raman frequency calculations were performed by using the BLYP functional [R] and the 6-G (d) basis set. The solvent effect is modelled by adopting the polarizable continuum model (PCM) [R]. The aggregation effect is considered by using quantum mechanics coupled with molecular mechanics (QM/MM) theory with two-layer ONIOM method [R]. The computational models were built from X-ray diffractions crystal structure, a cluster of molecules for HPS and 9 molecules for TPE. The molecule in centre was chosen as QM molecule and set as the high layer, whereas the remaining molecules around were treated as the MM molecules and defined as the low layer. The universal force field (UFF) was used for the MM part, and the molecules of MM part were frozen during the QM/MM geometry optimizations [R]. The electronic embedding are adopted in QM/MM calculations by incorporating the partial charges of the MM region into the quantum mechanical Hamiltonian [R5]. The NMR chemical shifts were calculated at the BLYP/GIAO/6-G (d) level [R6]. C and H relative chemical shifts (δ) were obtained in reference to tetramethylsilane (TMS) at the BLYP/ GIAO /6-+G (d,p) level [R7]. All the calculations were carried out by using Gaussian 9 program.

3 Figure S. ONIOM model and close look at the intermolecular packing structure with the intermolecular distances labeled in angstrom for HPS (top) and TPE (bottom).. Results and Discussion When in solution, 67 cm -, 6. (wavenumber and intensity respectively) (The same format is used for the following assignment). 67 cm -, 6. 5 cm -,.8 9 cm -, cm -,. 86 cm -,.8 7 cm -,.

4 55 cm -, cm -,. cm -, 6 cm -, cm -, cm -,.7 69 cm -, cm -, 6 When in cluster: 8 cm -, 6.5 cm -, 6 8 cm -, 6

5 cm -, cm -, cm -, 6 cm -,. 6 cm -,. 69 cm -,.7 cm -,.9 59 cm -,. 59 cm -,.8 6 cm -, cm -, 5 66 cm -, 6.9 Figure S. Each peak of simulated Raman spectra of TPE in Figure (a) has been assigned to the vibration of the TPE molecule. 5

6 When in solution, 7 cm -,.5 7 cm -,.5 77 cm -, cm -,.9 86 cm -,.5 98 cm -, 8. 6 cm -, cm -, cm -,.6 cm -,.65 9 cm -, 76 cm -,.9 85 cm -, cm -, cm -, 5 6

7 65 cm -, cm -, When in cluster, 6 cm -, cm -, 7. 5 cm -, cm -, cm -, cm -, cm -, 5. 9 cm -, 77.5 cm -, 8.6 7

8 88 cm -, 7. 5 cm -, cm -, 67 cm -,. 66 cm -, 75.6 Figure S. Each peak of simulated Raman spectra of HPS in Figure (b) has been assigned to the vibration of the HPS molecule. Degeneracy (a) C-NMR of TPE in solution C-NMR of TPE in cluster Chemical shift /ppm 8

9 Degeneracy (b) Solid Liquid Chemical shift / ppm Degeneracy (c) Si C-NMR of HPS in solution C-NMR of HPS in cluster Chemical shift /ppm Degeneracy (d) Solid Liquid 6 5 Chemical shift / ppm Figure S. Calculated (a) (c) and experimental (b) (d) (solid and liquid) NMR spectra of carbon atom for TPE (a)(b) and HPS (c)(d). Figure S shows the NMR data from simulation and experiment. From the calculated spectra in Figure S (a), we can see the peak position (chemical shift) appeared on the higher number for the TPE cluster when compared with its solution. In the meantime, the peaks in solution have separated into several small peaks for the cluster. Those phenomena were observed from the experimental spectra in Figure S (b). The main 9

10 peaks from the solid did appear at higher chemical shift than those from the liquid sample, which is in well agreement with the simulated spectra for carbon atoms at site and site, respectively. Compared with the sharp peaks in solution, which also agrees with the calculated spectrum, the broad peaks from the solid originate the overlap of several shoulder peaks. Note the solid sample usually shows a broad peak, which should be taken into account too. In Figures S(c) and S(d), similarly we observed the higher chemical shift in solid sample than in liquid sample, particularly in the range above 5 ppm, which should be assigned to carbon at site from the calculated data. References: [R] Becke, A. D. Density-Functional Thermochemistry. III. The Role of Exact Exchange. J. Chem. Phys. 99, 98, [R] Cossi, M.; Barone, V. Time-Dependent Density Functional Theory for Molecules in Liquid Solutions. J. Chem. Phys., 5, [R] Morokuma, K.; Wang, Q. F.; Thom, V. Performance Evaluation of the Three-Layer ONIOM method: Case Study for a Zwitterionic Peptide. J. Chem. Theory Comput. 6,, 7-. [R] Mayhall, N. J.; Raghavachari, K.; Hratchian, H. P. ONIOM-Based QM: QM Electronic Embedding Method Using Löwdin Atomic Charges: Energies and Analytic Gradients. J. Chem. Phys.,, 7. [R5] Lundberg, M.; Kawatsu, T.; Vreven, T.; Frisch, M. J.; Morokuma, K. Transition State in a Protein Environment ONIOM QM: MM Modeling of Isopenicillin N Synthesis. J. Chem. Theory Comput. 8, 5, -. [R6] Wolinski, K.; Hilton, J. F.; Pulay, P. Efficient Implementation of the Gauge-Independent Atomic Orbital Method for NMR Chemical Shift Calculations. J. Am. Chem. Soc. 99,, [R7]. Justino, L. L. G.; Ramos, M. L.; Abreu, P. E.; Carvalho, R. A.; Sobral, A. J.; Scherf, U.; Burrows, H. D. Conformational Studies of Poly(9, 9-dialkyfluorene)s in Solution Using NMR Spectroscopy and Density Functional Theory Calculations. J.

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