Electron-accepting dithiarubicene (emeraldicene) and derivatives prepared by unprecedented nucleophilic hydrogen substitution by alkyllithium reagents.

By understanding the role of DMF as a hydride source via a Pd-catalyzed reaction and switching to CH(3)CN solvent, an efficient route for the synthesis of emeraldicene and some new substituted derivatives is reported with potential application in organic electronics. Additionally, the nucleophilic alkylation of emeraldicene 4 a with alkyllithium reagents provides monosubstituted compounds 7 a and 7 b, the latter crystallizing in columnar stacks, with π-π overlap between adjacent molecules in the stack.