Electronic Communication within Flexible Bisdithiolene Ligands Bridging Molybdenum Centers

Bimetallic molybdenum dithiolene complexes involving two flexible ditopic conjugated linkers have been synthesized and characterized by electrochemistry, spectroelectrochemistry, and single crystal X-ray diffraction. The electrochemical investigations evidence that the two metallic bisdithiolene moieties are electronically coupled in the monocationic state. DFT and TD-DFT calculations further suggest that the intervalence charge transfer within both monocations is essentially localized on the ligand and can be described as an intraligand charge transfer (ILCT).