Hydration of Polycationic [5]Radialene with Quintuple 1,3-Dithiol-2-ylidenes Leads to a New Class of π-Extended Tetrathiafulvalene Scaffold.

[5]Radialene with quintuple 4,5-benzo-1,3-dithiol-2-ylidenes (DTs) easily forms a stable polycationic salt (1) (BF ) owing to its aromatic character in the central cyclopentadienide ring. In this work, it was found that the polycationic salt (1) underwent a hydration reaction in moist polar solvent to give several unexpected products, namely, an oxygen adduct dicationic salt (2) , a tetrathiafulvalene (TTF) vinylogue (3) with 1,4-dithiine-2(3H)-one moieties, and an oxygen adduct of π-extended TTF with a cyclopentenone core (4). Their molecular structures were fully determined by X-ray crystal-structure analysis.