Radical and diradical states of bis(molybdenocene dithiolene) complexes

The synthesis and characterization of two bis(dithiolene) proligands involving heteroatomic linkers such as 1,4-dithiine and dihydro-1,4-disiline between the two protected dithiolene moieties are described. Two bimetallic complexes involving these heteroatomic bridges between two redox active bis(cyclopentadienyl)molybdenum dithiolene moieties have been synthesized and characterized by electrochemistry, spectroelectrochemistry, and their properties rationalized with (TD-)DFT. Cyclic voltammetry experiments show sequential oxidation of the two redox centers with ΔE values between successive one-electron transfers varying according to the nature of the bridge. Depending on the nature of the heteroatomic bridge, the bis-oxidized complexes exhibit either a diradical character with both radicals essentially localized on the metallacycles, or a closed-shell dicationic state.