From molecular tinkertoys to inorganic-organic hybrid composites - functional materials featuring metal chalcogenide clusters

This dissertation is concerned with the chemistry of the hexarhenium selenide cluster and its use as a synthetic building block. Two themes underlay the research presented here: (1) to create of novel supramolecular arrays and (2) to provide possible solutions to problems associated with the synthesis of inorganic-organic hybrid materials.; Star-shaped scaffolding was used to develop a molecular Tinkertoy kit containing pieces which incorporate a variety of angles. Further functionalization of a molecular Tinkertoy based upon TPyP by incorporation of metal ions was discussed and examined along with the new electrochemical and photophysical properties observed. A new metallodendrimer motif containing clusters a the core, within the branches, and on the periphery was developed and discussed. Also addressed is the hitherto unseen electrochemical communication between [Re₆(μ₃-Se)₈]2+ clusters bridged by an organic moiety. Possible solutions to problems involved with the synthesis of inorganic-organic hybrid materials were provided, as well as a demonstration-of-feasibility synthesis demonstrating the successful copolymerization of [Re₆(μ₃-Se)₈]2+ vinylpyridine derivative with styrene.