Unearthing Periodicity in the Tuning of Chemical Reactivity by Lewis Acidic Metal Ions

James Blakemore, University of Kansas

Incorporation of Lewis acidic, redox-inactive metal ions into multimetallic structures has emerged as a viable strategy for systematic tuning of redox-active species. Most work in the field has examined redox catalysis by first-row transition metals, inspired by the presence of a redox-inactive Ca2+ ion in the oxygen evolving complex (OEC) of Photosystem II (PSII). However, although Lewis acidic metals have been shown to influence the properties of a variety of molecules and materials, comprehensive understanding of these effects is not yet available for metals beyond those of the first row of the transition series. Here, preparation and study of heterobimetallic macrocyclic complexes will be discussed with the goal of revealing the influence of periodicity on the tuning afforded by incorporation of redox-inactive Lewis acids into redox-active complexes. Specific examples with both later transition metals and the challenging uranyl ion will be discussed.