Supporting Information for: A Compactly Fused π Conjugated Tetrathiafulvalene Perylenediimide Donor Acceptor Dyad Michael Jaggi, a Carmen Blum, a Nathalie Dupont, b Jakob Grilj, b Shi-Xia Liu, *,a Jürg Hauser, a Andreas Hauser, b Silvio Decurtins a a Departement für Chemie und Biochemie, Universität Bern, Freiestrasse 3, CH-3012 Bern, Switzerland. b Département de chimie physique, Université de Genève, 30 quai Ernest-Ansermet, CH-1211 Genève 4, Switzerland. Email address: liu@iac.unibe.ch Table of Contents Experimental section Procedure for preparation of compound 1 S2 S3 1 H NMR Spectrum of compound 1 S4 Crystal packing of 1 Selected molecular orbitals for 1 Electronic absorption spectra of 1 upon electrochemical oxidation Decay curves in transient absorption upon pulsed irradiation at 400 nm S5 S6 S7 S7 S1
Experimental section Materials The compounds N-(1-octylnonyl)perylene-3,4,9,10-tetracarboxylic acid 3,4-anhydride-9,10- imide 2 7 and 5,6-diamino-2-(4,5-bis(propylthio)-1,3-dithio-2-ylidene)benzo[d]-1,3-dithiole 3 3e were prepared according to the literature procedures. All other chemicals and solvents were purchased from commercial sources and were used without further purification. Physical measurements 1 H NMR spectrum was measured at 400 MHz at 50 C. Chemical shifts δ were calibrated against TMS as an internal standard. FT-IR data were collected on a Perkin-Elmer Spectrum One spectrometer. UV-vis spectra were recorded on a Perkin-Elmer Lambda 900 spectrometer. Elemental analyses were performed on an Carlo Erba EA 1110 CHNS apparatus. Cyclic voltammetry was conducted on a VA-Stand 663 electrochemical analyzer. An Ag/AgCl electrode containing 2 M LiCl (in ethanol) served as reference electrode, a glassy carbon electrode as counter electrode, and a Pt tip as working electrode. Cyclic voltammetric measurements were performed at room temperature under N 2 in CH 2 Cl 2 (5 10-4 M) with 0.1 M n-bu 4 NPF 6 as supporting electrolyte. Mass spectrum was recorded on a FTMS 4.7T BioAPEX II for MALDI ionisation method. S2
Preparation of 1 A mixture of N-(1-octylnonyl)perylene-3,4,9,10-tetracarboxylic acid 3,4-anhydride-9,10- imide 2 (280 mg, 445 µmol), 5,6-diamino-2-(4,5-bis(propylthio)-1,3-dithio-2- ylidene)benzo[d]-1,3-dithiole 3 (117 mg, 270 µmol) and imidazole (700 mg, 10.3mmol) in pyridine (30 ml) was refluxed for 21 h at 135 C under N 2. After evaporation of pyridine, the purple residue was subjected to column chromatography on silica gel (CHCl 3 then 9:1 CHCl 3 :MeOH) to yield the crude product. This material was rechromatographed eluting initially with 8:2 CHCl 3 :CH 2 Cl 2, then with pure CHCl 3 and finally with 9:1 CHCl 3 :MeOH to afford analytically pure compound 1 as a deep-purple solid. Yield 54% (150 mg, 146 µmol). T > 223 C (dec.). Anal. Calc. for C 57 H 59 N 3 O 3 S 6 : C, 66.69; H, 5.79; N, 4.1. Found: C, 66.71; H, 5.97; N, 3.9%. 1 H NMR (CDCl 3, 50 C) δ 8.76 (d, J = 8.24 Hz, 2H), 8.58 (m, 6H), 8.22 (s, 1H), 7.50 (s, 1H), 5.11 (br, 1H), 2.70 (t, 4H), 2.17 (br, 2H), 1.83 (br, 2H), 1.59 (m, 4H), 1.19 (m, 24H), 0.95 (dt, 6H), 0.77 (t, 6H). Selected IR data (cm -1, KBr pellet): 3436 (br), 2922 (s), 2851 (m), 1693 (s), 1655 (s), 1591 (s), 1501 (w), 1437 (m), 1353 (m), 1340 (s), 1238 (m), 805 (m), 738 (m). MS (MALDI-TOF, DCTB as matrix, positive) calcd. for C 57 H 59 N 3 O 3 S 6 1025.29, found 1025.29. Single crystals suitable for X-ray analysis were obtained by slow evaporation of a CH 2 Cl 2 solution (~150 µg/ml) of 1. S3
S4 1 H NMR Spectrum of 1 in CDCl 3 1.9775 6.0505 1.0491 1.0033 1.0082 3.9998 2.0588 2.0372 4.0538 23.950 6.0123 6.0714 8.6015 8.5809 8.5568 8.5365 8.2182 7.5046 7.1806 5.1148 2.7225 2.7142 2.7047 2.6965 2.6864 2.6782 2.2187 2.1966 2.1571 2.1392 2.1194 1.8393 1.8256 1.8058 1.7918 1.6226 1.6157 1.6044 1.5976 1.5861 1.5796 1.5681 1.5614 1.5503 1.3991 1.1930 1.1581 0.9706 0.9635 0.9523 0.9452 0.9339 0.9267 0.7826 0.7658 0.7482 0.0000 (ppm) 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 1.9775 6.0505 1.0491 1.0033 8.7667 8.7461 8.6261 8.6015 8.5809 8.5568 8.5365 8.2182 7.5046 (ppm) 7.6 7.8 8.0 8.2 8.4 8.6 8.8
Figure S1. Crystal packing of 1 showing the hydrogen bondings (dashed lines) within the dimers. S5
The DFT method was employed with the B3LYP functional and the TZVP (valence triplezeta plus polarization) basis set. The calculations were done with the TURBOMOLE V5.10 program package. The ground-state molecular geometry of 1 was constrained to have C s symmetry. Figure S2. Selected molecular orbitals for 1. Ref Ref: (a) Treutler, O.; Ahlrichs, R. J. Chem. Phys. 1995, 102, 346. (b) Bauernschmitt, R.; Ahlrichs, R. Chem. Phys. Lett. 1996, 256, 454. (c) Bauernschmitt, R.; Häser, M.; Treutler, O.; Ahlrichs, R. Chem. Phys. Lett. 1997, 264, 573. S6
Figure S3. Electronic absorption spectra of 1 upon electrochemical (V = 0.8 V vs. Ag/AgCl) oxidation. Figure S4. Decay curves in transient absorption upon pulsed irradiation at 400 nm, detected at different wavelengths. The decay is non-exponential with a first time constant of 1 ps and a second time constant of 10 ps. S7