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A series of conjugated polymer−redox polymer hybrids based on the complexation of poly-(bibenzimidazoles) with bis-(2,2‘-bipyridyl)Ru 2+ and bis-(2,2‘-bipyridyl)Os 2+ has been prepared to investigate the effects of electronic communication between metal centers through the conjugated backbone. Electron transport rates in the mixed valence M(III/II) states have been measured as electron diffusion coefficients ( D e ) by impedance spectroscopy and dual (sandwich) electrode voltammetry. D e values are generally higher than for nonconjugated Ru(2,2‘-bipyridyl) 3 3+/2+ -type polymers, and their dependencies on the metal (Os or Ru), pH and nature of the polymer backbone are consistent with significant contributions from superexchange mechanisms. Hole-type superexchange appears to dominate in the Ru polymers, while a number of observations indicate that electron-type superexchange may dominate for the Os complexes.
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Cameron et al. (2001) studied this question.
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