Synthesis and Electropolymerization of Distyrylbipyridine and Methyldistyrylbipyridine Complexes of Iron, Ruthenium, Osmium, Rhenium, and Cobalt

摘要

Several dozen Fe, Ru, and Co complexes containing the ligands 4,4-distryl-2.2'-bipyridine (DSB) and 4.4'-bis(p-methylstyryl)-2.2'-bipyridine (MeDSB) have been prepared. The ligands undergo coupling reactions when the complexers are reduced electrochemically, resulting in the formation of smooth and adherent electroactive polymeric films on Pt electrodes. Evaluation of the relative rates of electropolymerization for selected metal complex monomers shows that the DSB and MeDSB ligands lead to slower electropolymerizations than do the related ligands vbpy (4-vinyl-4'-riethyl-2.2'-bipyridine) and vpy (4-vinylpyridine) in analogous complexes. The stability of the DSB and MeDSB ligands was helpful in the synthesis of novel electropolymerizable monomers such as Os(DSB)32+, Os(MeDSB)32+, (DSB)2M(CO)C1+ (M = Ru, Os), and (DSB)Re(CO)3X. The last complex is a C02 reduction catalyst. Correlations between monomer composition and polymer characteristics were revealing, showing, for example, that poly-(MeDSB)3M2+ films exhibit faster electron transport and are more permeable than previously studied poly-Ru(vbpy)32+ films.