2013 Volume 86 Issue 8 Pages 927-939
New tetrathiafulvalene (TTF)-type electron-donor molecules annelated with imidazole or benzimidazole moiety were designed and synthesized by the phosphite-mediated coupling reactions of imidazole- or benzimidazole-annelated 1,3-dithiole-2-thiones. The effect of imidazole-annelation on the redox properties was evaluated by theoretical calculation and electrochemical measurement, and the imidazole-annelation slightly enhances the electron-donating abilities of parent TTF and benzo-TTF skeletons. The substitution of the imidazole ring with an electron-withdrawing cyano group caused a large high potential shift of the oxidation potentials in the cyclic voltammetry and an intense intramolecular charge-transfer absorption band in the electronic spectrum. The self-assembling ability was investigated by crystal structure analysis, where solvent or counter anion mediated one-dimensional hydrogen-bonded arrays of imidazole rings were linked through π-stacks and S···S interactions to construct multidimensional networks. The donor molecules afforded weak charge-transfer complexes with tetracyanoquinodimethane (TCNQ) and fully ionic complexes with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) and 2,3,5,6-tetrafluoro-TCNQ. In the crystal structures of TCNQ complex and iodine salt of a benzimidazole-annelated derivative, π-stacking motifs, donor–acceptor alternating stack, and π-stacking dimer, respectively, were interacted through hydrogen-bonds.
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