Resolving orbital pathways for intermolecular electron transfer.

ABSTRACT: Over 60 years have passed since Taube deduced an orbital-mediated electron transfer mechanism between distinct metal complexes. This concept of an orbital pathway has been thoroughly explored for donor-acceptor pairs bridged by covalently bonded chemical residues, but an analogous pathway has not yet been conclusively demonstrated for formally outer-sphere systems that lack an intervening bridge. In our present study, we experimentally resolve at an atomic level the orbital interactions necessary for electron transfer through an explicit intermolecular bond. This finding was achieved using a homologous series of surface-immobilized ruthenium catalysts that bear different terminal substituents poised for reaction with redox active species in solution. This arrangement enabled the discovery

SUBMITTER: Kellett CW 

PROVIDER: S-EPMC6249235 | biostudies-literature | 2018 Nov

REPOSITORIES: biostudies-literature