Supporting Information for: Optical Activity of Heteroaromatic Conjugated Polymer Films Prepared by

Transcription

1 upporting Information for: ptical Activity of Heteroaromatic Conjugated Polymer Films Prepared by Asymmetric Electrochemical Polymerization in Cholesteric Liquid Crystals: tructurally Induction Function Kohsuke Kawabata, Masaki Takeguchi, and Hiromasa Goto * Division of Materials cience, Faculty of Pure and Applied ciences, University of Tsukuba, Tsukuba, Ibaraki, , Japan, Microstructure Characterization Platform Promotion ffice, ational Institute for Materials cience, Tsukuba, Ibaraki, , Japan * Corresponding author. Tel.: ; fax: ; gotoh@ims.tsukuba.ac.jp 1

2 General methods Differential scanning calorimetry (DC) measurement was carried out with a rate of 5 ºC min 1 with EXTRA 7000 (Hitachi). The ultraviolet-visible near-infrared (UV-vis-IR) absorption spectra were taken with UV-3100PC (himadzu). The CD spectra of the polymer films deposited on IT glasses were taken with J-720 (Jasco). Linear dichroism signals of the polymers were evaluated (to be negligible intensity) and removed from the CD spectra. The infrared (IR) absorption spectra were obtained with FT/IR 550 (JAC) by using the KBr method. Matrix-assisted laser desorption ionization time-of-flight mass spectroscopy (MALDI-TF-M) analysis was conducted using TF/TF 5800 (AB ciex). MALDI-TF-M spectra of PEDT, poly(bis-edt), and the furan containing polymers somehow could not be obtained, which is maybe due to their high molecular weight. The polymer films were scratched off the IT substrates and mixed with dithranol used as a matrix in THF solution. canning electron microscopic observation was carried out with JM-7000F (Jeol). Polarizing optical microscopy was performed with ECLIPE LV100 (ikon). 1 H and 13 C MR spectra were recorded on JM-EC 400 (Jeol). The chemical shifts in deuterated chloroform were reported against tetramethylsilane internal standard. Calculations The spin densities of the monomers in the radical cationic state and the optimized geometry for model compounds were calculated by density functional theory (DFT) method at Becke s three-parameter set with Lee-Yang-Parr correlation functional (B3LYP) with 6-31G* basis set, which is implemented in partan 04 package. Energy profiles for inter-ring rotation of 4DMBT and 3DMBT in the neutral and radical cationic were calculated by the DFT method with variation of the interring C=C C=C dihedral angles from 0 º to 180 º with a step of 10 º. 2

3 (a) (e) (h) (k) (b) (m) (o) (q) (u) (s) (f) (i) (l) (c) (n) (g) (p) (r) (t) (v) (j) (d) Figure 1. pin density on each atom of BT (a), 3DMBT (b), 4DMBT (c), TMBT (d), ter-t (e), TT (f), bis-tt (g), T-IT (h), EDT (i), bis-edt (j), T-Fl (k), F-Fl (l), T-Cz1 (m), F-Cz1 (n), T-Dbt (o), F-Dbt (p), T-Bp (q), F-Bp (r), 3,6T-Cz1 (s), TT-Btdaz (t), T-Btdaz (u), and F-Btdaz (r) in the radical cationic state calculated by DFT method (B3LYP-6-31G*) (Red colored sites indicate the most reactive sites. Hydrogen atoms are omitted for simplification.)

4 1st cooling CC+6CB CC+6CB+BT+TBAP Cr CLC Iso Exothem. Cr CLC Iso 2nd heating Temperature / o C Figure 2. DC curves for the CLC medium (black) and the CLC electrolyte solution containing BT (red). Cr and Iso denote crystal and isotropic phases, respectively. 4

5 Figure 3. IR spectra of the monomers and the polymers prepared in the CLC. BT and poly(bt) (a), ter-t and poly(ter-t) (b), 4DMBT and poly(4dmbt) (c), 3DMBT and poly(3mbt) (d), TMBT and poly(tmbt) (e), T-IT and poly(t-it) (f), EDT and PEDT (g), bis-edt and poly(bis-edt) (h), TT and poly(tt) (i), and bis-tt and poly(bis-tt) (j). 5

6 Figure 4. IR spectra of the monomers and the polymers prepared in the CLC. T-Fl and poly(t-fl) (a), T-Cz1 and poly(t-cz1) (b), T-Dbt and poly(t-dbt) (c), T-Bp and poly(t-bp) (d), F-Fl and poly(f-fl) (e), F-Cz1 and poly(f-cz1) (f), F-Dbt and poly(f-dbt) (g), F-Bp and poly(f-bp) (h), 3,6T-Cz1 and poly(3,6t-cz1) (i), F-Btdaz and poly(f-btdaz) (j), T-Btdaz and poly(t-btdaz) (k), and TT-Btdaz, poly(tt-btdaz) (l). 6

7 (a) Absorbance / arb. units (b) (c) (d) (e) (f) Wavenumber / cm Figure 5. IR spectra of poly(ter-t) prepared in the CLC (a), poly(ter-t) in an acetonitrile solution (b), ter-t (c), 6CB (d), CC (e), and TBAP (f). 7

8 Figure 6. MALDI-TF-M spectra of poly(bt) (a), poly(3dmbt) (b), poly(ter-t) (c), poly(4dmbt) (d), poly(t-it) (e), poly(tmbt) (f), and poly(bis-tt) (g). 8

9 Figure 7. MALDI-TF-M spectra of poly(t-fl) (a), poly(3,6t-cz1) (b), poly(t-cz1) (c), poly(t-btdaz) (d), poly(t-dbt) (e),and poly(tt-btdaz) (f). 9

10 Figure 8. ptimized geometry of the model oligomers for poly(bt) (top view (a) and side view(b)), poly(4dmbt) (top view (c) and side view (d)), and poly(tmbt) (top view (e) and side view (f)) in the neutral state calculated by DFT method (B3LYP-6-31G*). 10

11 Figure 9. PM images for contact method between CP/6CB and CC/6CB (a) and ()-8BpB6/6CB and CC/6CB (b). 11

12 LD / D Absorbance / nm Figure 10. Linear dichroism spectrum (top) and UV-vis absorption spectrum (bottom) of poly(bt) prepared in CLC consisting of 6CB and CC. 12