The oxygen evolving complex (OEC) of photosystem II is responsible for the four-electron oxidation of water to dioxygen in oxygenic photosynthetic organisms. These organisms use light to drive this thermodynamically uphill process to harvest high-energy electrons from water for cellular energy, generating O<sub>2</sub> as a byproduct. While numerous details of the operation of the OEC are well understood, the molecular mechanism of O=O formation remains under debate. Model complex chemistry from our group will be presented wherein we have prepared cluster systems with little or no terminal multidentate ligation in order to generate geometrically flexible and reactive clusters. Two systems will be presented: a series of Ca-Mn-O hemicubane clusters with variable calcium content, and their electrocatalytic activity in activation of water in oxidation reactions, and a Mn cubane cluster with a pendant Mn=O moiety that evolves dioxygen from an oxidation state analagous to the turnover state of the natural system.

Geometrically flexible synthetic manganese-oxygen and calcium-manganese-oxygen cubane clusters as reactive biomimics of the oxygen evolving complex of photosystem II

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.