We have been interested in molecular systems that display rich metal-ligand redox interplay and possess intraligand donor-acceptor (D-A) interactions due to their direct relevance in enzymatic catalysis and molecular electronics.  Here, we use a combined spectroscopic and computational approach to probe low-lying charge transfer states in transition metal complexes that possess D-A ligands.  We use a Valence Bond Configuration Interaction model to understand the electronic origin of the exchange interaction (J) and electronic coupling matrix element (HDA) in D-A biradicals.   Additionally, we show that the magnitude of the hyperfine interaction can probe spin delocalization and charge transfer character in these biradical systems.  Finally, we will describe how valence delocalization can result in ferromagnetic alignment of localized radical spins separated by over 22 �.  Such ferromagnetic coupling is promoted by organic mixed-valency and provides keen insight into the ability of single molecules to communicate spin information over nanoscale distances.

Donor-acceptor ligands in inorganic chemistry:  The influence of excited states on ground state properties

243rd National Meeting (2012)

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