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[摘要]：New tetrathiafulvalene (TTF)-based electron-donor molecules having 4,4'- and 2,2'-biimidazole units (1 and 2, respectively) as hydrogen bonding units were designed and synthesized. Cyclic voltammetry showed that both 1 and 2 possess strong electron-donating abilities close to that of TTF with two-stage reversible redox processes. In the crystal structure of 1, uniform p stacking, side-by-side S...S interactions of the TTF moiety, and multiple hydrogen bonds of the biimidazole unit via crystalline water molecules contribute to the formation of a two-dimensional donor layer. The crystal structure of 2 was constructed by one-dimensional ribbons formed by complementary hydrogen bonds characteristic to 2,2'-biimidazole and side-by-side S...S interactions on the TTF moiety. In the charge-transfer salt of 2 with iodine, which included the (I82)n one-dimensional comb-like structure as the anion part, the NH...I hydrogen bond anchored the donor molecule in the cavity of the (I82)n chain. Complex formation of 1 and 2 with tetracyanoquinodimethane afforded mixed-valence charge-transfer complexes showing semiconducting behaviors (room temperature conductivities = 103 and 101 S?cm1, respectively). |
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