MODEL COORDINATION-COMPLEXES FOR DESIGNING POLY(TERTHIOPHENE) RH(I) HYBRID MATERIALS WITH ELECTROCHEMICALLY TUNABLE REACTIVITIES/

The synthesis and characterization of two chiral, redox-active Rh(I) b is(diphenylphosphinite) monomers, complexes 3 and 4, are reported. Com plex 4, o-6-(3'-alpha-terthiophene)Rh(I)(eta(4)-C7H8)]BF4, can be elec trochemically polymerized to form poly-4, and the eta(4)-C7H8 ligand c an be hydrogenated in THF to form the metal-containing polymer 17. Pol ymer 17 is proposed to consist of a poly(terthiophene) backbone with R h(I) phenyl-bridged dimers acting as cross-linkers between neighboring polymer chains. This structural formulation for polymer 17 is based u pon its electrochemistry and a comparison with the solution chemistry of monomer 4. Significantly, this study discusses the importance of ba lancing polymerization potential, metal oxidation potential, and polym er ligating properties in the design of high surface area, polymeric, redox-switchable hemilabile ligands.