Diisocyanoarene-linked pentacarbonylvanadate(I-) ions as building blocks in a supramolecular charge-transfer framework assembled through noncovalent π-π and contact ion interactions.

Three synthetic routes to the unusual supramolecular complex ([Cp(2)Co](2)[{(OC)(5)V}(2)(µ-1,4-CNC(6)Me(4)NC)])(∞), which was crystallographically characterized, are presented. The dianion [{(OC)(5)V}(2)(µ-1,4-CNC(6)Me(4)NC)](2-) constitutes the first subvalent organometallics featuring a diisocyanoarene linker.