Dichalcogen-Bridged Acenaphthenes as New Electron Donors

Three new electron donors, 5,6-dihydroacenaphtho[5,6-cd]-1,2-dithiole (1a), -diselenole (1b), and -ditellurole (1c) have been prepared with a view to developing new electron donors for low-dimensional molecular complexes. Their donor characters are markedly enhanced as compared with the corresponding dichalcogen-bridged naphthalenes. They formed charge-transfer complexes with tetracyanoquinodimethane (TCNQ). Their electrical conductivities increase in the order of polarizable chalcogen. The crystal structures of 1a–TCNQ complex and neutral 1c were determined by X-ray analyses. In the crystal, 1a and TCNQ form a unique mixed stack, that is, a pair of donors and a pair of acceptors make an alternately stacking column. Neutral 1c takes an almost planar conformation and molecules are connected to each other with strong Te–Te interactions.