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. Tuning of the properties of actinide elements with heterobimetallic effects is an especially attractive target, considering the importance of redox processing of these elements for nuclear fuel preparation and recycling. In this talk, preparation and study of heterobimetallic macrocyclic uranyl (UO22+) complexes will be discussed. Quantitative metrics regarding the tuning afforded by incorporation of redox-inactive metals will be discussed, as well as recent results examining the role of macrocycle structure and supramolecular ion-binding preferences in optimization of electron transfer rates.
Thursday, June 10, 2021 - 3:30pm
Prof. James Blakemore
University of Kansas