Synthesis and spectroscopic properties of chial binaphtyl-linked subphthalocyanines

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1 Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Synthesis and spectroscopic properties of chial binaphtyl-linked subphthalocyanines Luyang Zhao, a,b Kang Wang, b Taniyuki Furuyama, a Jianzhuang Jiang* b and Nagao Kobayashi* a a Department of Chemistry, Graduate School of Science, Tohoku University nagaok@m.tohoku.ac.jp b Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing jianzhuang@ustb.edu.cn Supporting information Table of Contents General Comments S 1 Additional Experimental Results S 2 Full Experimental Procedures S 4 Full Computational Details S 5 References S 11

2 General Comments Unless otherwise noted, solvents and reagents were purchased from Tokyo Kasei Co. and Wako Chemicals Co. and were used after appropriate purification (distillation or recrystallization). Electronic absorption spectra were recorded on a JASC V-570 spectrophotometer. Magnetic circular dichroism (MCD) spectra were obtained on a JASC J-725 spectrodichrometer equipped with a JASC electromagnet capable of producing magnetic fields of up to 1.03 T (1 T = 1 tesla) with both parallel and antiparallel fields. The magnitudes were expressed in terms of molar ellipticity per tesla ([θ] M / deg dm 3 mol 1 cm 1 T 1 ). Fluorescence spectra in the UV-vis region were obtained on a HITACHI F-4500 spectrofluorometer. Absolute fluorescence quantum yields were measured on a Hamamatsu C G calibrated integrating sphere system. NMR spectra were obtained on a Bruker AVANCE III 500 spectrometer. Unless otherwise noted, samples were recorded in CDCl 3. Chemical shifts are expressed in δ (ppm) values, and coupling constants are expressed in hertz (Hz). 1 H-NMR spectra were referenced to the residual solvent as an internal standard. The following abbreviations are used: s = singlet, d = doublet, t = triplet, and m = multiplet. High-resolution mass spectra (HRMS) were recorded on a Bruker Daltonics Apex-III spectrometer. Cyclic voltammetry (CV) measurements were recorded with a Hokuto Denko HZ5000 potentiostat under a nitrogen atmosphere in solutions with 0.1 M of tetrabutylammonium perchlorate (TBAP) as supporting electrolyte. Measurements were made with a glassy carbon (GC) electrode (area = 0.07 cm 2 ), an Ag/AgCl reference electrode, and a Pt wire counter electrode. The concentration of the solution was fixed at 1.0 mm and the sweep rates were set to 100 mv/s. S-1

3 Additional Experimental Results Figure S1. bserved high-resolution mass spectrum (top) of 1S and the theoretical isotropic distribution pattern for C 84 H 42 BClN 6 6 ([M] + ) (bottom). S-2

4 Figure S2. 1 H- 1 H CSY spectrum of 1S in CDCl 3. Figure S3. Cyclic voltammogram of 1 in CH 2 Cl 2 containing 0.1 M [NBu 4 ][Cl 4 ] at scan rate of 40 mv s -1. S-3

5 Full Experimental Procedures Materials (S)/(R)- benzo[b]dinaphtho[2,1-e:1,2 -g][1,4]-dioxocine-5,6-dicarbonitrile were synthesized according to published procedures. i Synthesis of SubPc (1S/R) CN CN BCl 3 (1 eq) 1,2,4-trichlorobenzene, reflux, 4 h N N N N Cl B N N 1S/R 33% 1.0 M CH 2 Cl 2 solution of boron trichloride (1.0 ml, 1.0 eq) was added to a 1,2,4-trichlorobenzene solution (5.0 ml) of (R)/(S)-2 (410 mg, 1.0 mmol) at room temperature. The resultant mixture was gradually heated to reflux under nitrogen for 4 h. After removal of the solvent, the resultant solid was chromatographed on a silica gel column using CHCl 3 as eluent. Repeated chromatography followed by recrystallization from CHCl 3 and MeH gave 1 as a red powder (174 mg, 33%). 400 MHz 1 H-NMR (CDCl 3 ) δ (ppm): 8.80 (s, 3H), 8.73 (d, 3H), 8.10 (d, 3H), 8.01 (d, 3H), (m, 9H), (m, 9H), (m, 12H). HRMS-MALDI Calcd for C 84 H 42 BClN 6 6 [M] Found: Anal. Calcd (%) for (R)-C 84 H 42 BClN 6 6 CH 3 H: C, 77.96; H, 3.54; N, 6.42; Found: C, 77.82; H, 3.59; N, 6.38 and for (S)-C 84 H 42 BClN 6 6 2CH 3 H: C, 76.99; H, 3.76; N, 6.26; Found: C, 76.81; H, 3.74; N, UV vis (CHCl 3 ) λ max (10-4 ε): 573 nm (9.8). λ FL, max (CHCl 3 ): 585 nm. Φ FL = 0.25, λ FL, max (CHCl 3 ): 585 nm. S-4

6 Full Computational Details Computational Details Geometry optimization for all molecules was performed at the DFT level, by means of the hybrid Becke3LYP ii (B3LYP) functional as implemented in Gaussian iii The 6-31G* basis set was used for the all atoms. After the geometry optimization, the time-dependent (TD) DFT calculations iv were performed to evaluate the stick absorption spectrum employing with the same theory and basis set. All stationary points were optimized without any symmetry assumptions and characterized by normal coordinate analysis at the same level of the theory (the number of imaginary frequency, Nimag, 0). Cartesian Coordinates and Total Electron Energies 1S SCF Done: E(RB3LYP) = A.U Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S-5

7 S-6

8 TD DFT output HM: 329, LUM: 330 Excited State 1: Singlet-E ev nm f= <S**2>= > > > This state for optimization and/or second-order correction. Total Energy, E(TD-HF/TD-KS) = Copying the excited state density for this state as the 1-particle RhoCI density. Excited State 2: Singlet-E ev nm f= <S**2>= > > > Excited State 3: Singlet-A ev nm f= <S**2>= > > > > Excited State 4: Singlet-E ev nm f= <S**2>= > > > > > > S-7

9 Excited State 5: Singlet-E ev nm f= <S**2>= > > > > > > Excited State 6: Singlet-A ev nm f= <S**2>= > > > > Excited State 7: Singlet-E ev nm f= <S**2>= > > > > > Excited State 8: Singlet-E ev nm f= <S**2>= > > > > > Excited State 9: Singlet-A ev nm f= <S**2>= > > > > > > Excited State 10: Singlet-E ev nm f= <S**2>= > > > > > > > Excited State 11: Singlet-E ev nm f= <S**2>= > > > > > > > Excited State 12: Singlet-E ev nm f= <S**2>= > > > > Excited State 13: Singlet-E ev nm f= <S**2>= > > > > Excited State 14: Singlet-A ev nm f= <S**2>=0.000 S-8

10 324 -> > > > Excited State 15: Singlet-A ev nm f= <S**2>= > > > > > > > Excited State 16: Singlet-A ev nm f= <S**2>= > > > > > > > > > Excited State 17: Singlet-A ev nm f= <S**2>= > > > > > > > > > Excited State 18: Singlet-A ev nm f= <S**2>= > > > Excited State 19: Singlet-E ev nm f= <S**2>= > > > > Excited State 20: Singlet-E ev nm f= <S**2>= > > > > Excited State 21: Singlet-A ev nm f= <S**2>= > > > > Excited State 22: Singlet-E ev nm f= <S**2>= > > Excited State 23: Singlet-E ev nm f= <S**2>= > > S-9

11 Excited State 24: Singlet-E ev nm f= <S**2>= > > Excited State 25: Singlet-E ev nm f= <S**2>= > > S-10

12 References for Supporting Information i Wang, K.; Qi, D.; Wang, H.; Cao, W.; Li, W.; Jiang, J. Chem. Eur. J. 2012, 18, ii (a) Becke, A. D. Phys. Rev. 1988, A38, (b) Becke, A. D. J. Chem. Phys. 1993, 98, (c) Becke, A. D. J. Chem. Phys. 1993, 98, (d) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. 1988, B37, iii Gaussian 09, Revision C.01, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao,.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.; Peralta, J. E.; gliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev,.; Austin, A. J.; Cammi, R.; Pomelli, C.; chterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; rtiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc., Wallingford CT, iv (a) Bauernschmitt, R. d.; Ahlrichs, R. Chem. Phys. Lett. 1996, 256, (b) Dreuw, A.; Head-Gordon, M. Chem. Rev. 2005, 105, S-11