CAS: Exploiting Spin in Photo-induced Chemistry: Fundamental Explorations of High-spin and Low-spin Transition Metals in Long-lived Charge Separated States and Oxidative Catalysis

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In this project funded by the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Professors Amanda Morris and Gordon Yee of the Department of Chemistry at Virginia Polytechnic Institute and State University are exploring the role of molecular spin state on photochemistry. The proposed work constitutes a systematic study of molecular reorganization and spin at molecule-metal oxide interfaces and has the potential to impact research areas across various application spaces including photocatalysis, photovoltaics, and quantum information sciences. The interdisciplinary project brings together knowledge in molecular inorganic, materials, and photophysical chemistry providing a broad foundation for educational enrichment at the K-12 and collegiate levels. Outreach, including efforts to promote diversity in science, will be a component of the funded work.Long-lived, charge-separated states are critical to the realization of both photovoltaic and photocatalytic assemblies. The proposed research is motivated by the need to understand the role of molecular reorganization and metallic spin state in controlling charge-separated-state lifetimes and catalytic selectivity/efficiency. The research builds on their recent work exploring charge-transfer-induced spin-crossover compounds and the impact of the accompanying molecular reorganizations on photoinduced electron transfer processes. The results gathered from the proposed studies will enable the development of structure–function relationships with respect to spin and reorganization energies in photo-induced reactivity that, thus far, have been relatively unexplored. They aim to answer the following questions: What is the role of high-spin/low-spin electronic state transitions on photo-induced charge separated lifetimes? Can the design principles uncovered in the previous aim be extended to more severe molecular reorganizations, i.e., intermolecular and intramolecular ligand association/dissociation? Does molecular spin state control photocatalytic mechanisms, i.e., rate and path?This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.