A Compactly Fused π Conjugated Tetrathiafulvalene Perylenediimide Donor Acceptor Dyad

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1 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. 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

2 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 ( 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

3 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 , found 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

4 S4 1 H NMR Spectrum of 1 in CDCl (ppm) (ppm)

5 Figure S1. Crystal packing of 1 showing the hydrogen bondings (dashed lines) within the dimers. S5

6 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

7 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