The Supporting Information for Synthesis and Unique Optical Properties of Selenophenyl BODIPYs and Their Linear Oligomers Daisuke Taguchi, 1 Takashi Nakamura, 1 Hiroaki Horiuchi, 2 Makoto Saikawa, 1 Tatsuya Nabeshima 1, * 1. Graduate School of Pure and Applied Sciences and Tsukuba Research Center for Energy Materials Science (TREMS), University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan 2. Division of Molecular Science, Graduate School of Science and Technology, Gunma University, 1-5-1 Tenjin-cho, Kiryu, Gunma 376-8515, Japan * E-mail: nabesima@chem.tsukuba.ac.jp TEL & FAX: +81-(0)-29-853-4507 1 / 21
Table of contents 1. NMR spectra...3 2. ESI TOF mass spectra... 14 3. Cyclic voltammetry... 17 4. Singlet O2 generation... 18 5. X-ray crystallography... 19 6. References for the Supporting Information... 21 2 / 21
1. NMR spectra Figure S1. 1 H NMR spectrum of SB1a (CDCl3, 400 MHz). Figure S2. 13 C NMR spectrum of SB1a (CDCl3, 151 MHz). 3 / 21
Figure S3. 1 H NMR spectrum of SB1b (CDCl3, 400 MHz). Figure S4. 13 C NMR spectrum of SB1b (CDCl3, 151 MHz). 4 / 21
Figure S5. 1 H NMR spectrum of SB1c (CDCl3, 400 MHz). Figure S6. 13 C NMR spectrum of SB1c (CDCl3, 151 MHz). 5 / 21
Figure S7. 1 H NMR spectrum of 7 (CDCl3, 400 MHz). Figure S8. 13 C NMR spectrum of 7 (CDCl3, 101 MHz). 6 / 21
Figure S9. 1 H NMR spectrum of 8 (CDCl3, 400 MHz). Figure S10. 13 C NMR spectrum of 8 (CDCl3, 101 MHz). 7 / 21
Figure S11. 1 H NMR spectrum of SB1d (CDCl3, 400 MHz). Figure S12. 13 C NMR spectrum of SB1d (CDCl3, 151 MHz). 8 / 21
Figure S13. 1 H NMR spectrum of SB1e (CDCl3, 300 MHz). Figure S14. 13 C NMR spectrum of SB1e (CDCl3, 151 MHz). 9 / 21
Figure S15. 1 H NMR spectrum of SB2a (CDCl3, 600 MHz). Figure S16. 13 C NMR spectrum of SB2a (CDCl3, 151 MHz). 10 / 21
Figure S17. 1 H NMR spectrum of SB3a (CDCl3, 400 MHz). 11 / 21
Figure S18. 13 C NMR spectrum of SB3a (CDCl3, 151 MHz). 12 / 21
a,c b g d,e h f 145 CDCl 3 h g f e d N Se F a c b B N F Se 140 δ / ppm 8 4 0 Figure S19. 1 H 19 F HOESY spectrum of SB1a (CDCl3, 600 MHz). δ / ppm 13 / 21
2. ESI TOF mass spectra Figure S20. Experimental (top) and calculated (bottom) mass spectra for SB1a ([M+Na] + ) obtained by HRMS (ESI). Figure S21. Experimental (top) and calculated (bottom) mass spectra for 7 ([M+H] + ) obtained by HRMS (ESI). 14 / 21
Figure S22. Experimental (top) and calculated (bottom) mass spectra for 8 ([M+Na] + ) obtained by HRMS (ESI). Figure S23. Experimental (top) and calculated (bottom) mass spectra for SB1e ([M+Na] + ) obtained by HRMS (ESI). 15 / 21
Figure S24. Experimental (top) and calculated (bottom) mass spectra for SB2a ([M+Na] + ) obtained by HRMS (ESI). 16 / 21
3. Cyclic voltammetry Figure S25. Cyclic voltammogram of SB1a (CH2Cl2, 100 mm (nbu4n)(pf6)) Figure S26. Cyclic voltammogram of TB1a (CH2Cl2, 100 mm (nbu4n)(pf6)) 17 / 21
4. Singlet O2 generation Figure S27. Phosphorescence spectrum of singlet oxygen sensitized by SB2a in air-saturated CHCl3 at room temperature. 18 / 21
5. X-ray crystallography Single-crystal X-ray crystallographic measurements were performed using a Bruker APEX II ULTRA with MoKa radiation. The collected diffraction images were processed by Bruker APEX2. The initial structure was solved using SHELXS-2013 [S1] and refined using SHELXL-2016 [S2], which were running on Yadokari-XG crystallographic software [S3]. Disordered selenophenyl rings were refined with DFIX and RIGU restraints. Carbon atoms of the disordered selenophenyl rings were refined isotropically, because these atoms were located close to the Se atoms of the other disordered set and anisotropic refinement was difficult. CCDC 1822457 (SB1a) contains the data for the structures. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures. Single crystal of SB1a suitable for X-ray diffraction analysis was obtained by slow evaporation of chloroform solution of SB1a. Crystal data for SB1a: C26H21BF2N2Se2, Fw = 568.19, black block, 0.44 0.40 0.08 mm 3, monoclinic, space group P21/c (No. 14), a = 13.2178(5) Å, b = 12.0114(5) Å, c = 14.7654(6) Å, b = 107.360(1), V = 2237.44(16) Å 3, Z = 4, T = 96 K, l(moka) = 0.71073 Å, qmax = 30.672, R1 = 0.0398, wr2 = 0.1492, GOF = 1.206. CCDC No. 1822457. 19 / 21
Figure S28. The molecular structure of SB1a determined by X-ray crystallography. Ellipsoidal model (50% probability). Hydrogen atoms were omitted for clarity. C, light green; N, blue; B, pink; F, yellow green; Se, orange. The selenophene rings were disordered, and a major conformer is shown. 20 / 22
6. References for the Supporting Information 1. Sheldrick, G. M. Acta Cryst. 2008, A64, 112 122. 2. Sheldrick, G. M. Acta Cryst. 2015, C71, 3 8. 3. (a) Wakita, K. Yadokari-XG, Software for Crystal Structure Analyses, 2001; (b) Kabuto, C.; Akine, S.; Nemoto, T.; Kwon, E. J. Cryst. Soc. Jpn. 2009, 51, 218 224. 21 / 21