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

在这个由化学部化学结构、动力学和机理B项目资助的项目中，弗吉尼亚理工学院和州立大学化学系的Amanda Morris教授和Gordon Yee教授正在探索分子自旋态在光化学中的作用。提出的工作构成了分子-金属氧化物界面的分子重组和自旋的系统研究，并有可能影响各种应用领域的研究领域，包括光催化、光伏和量子信息科学。该跨学科项目汇集了分子无机、材料和光物理化学方面的知识，为K-12和大学水平的教育提供了广泛的基础。推广工作，包括促进科学多样性的努力，将是受资助工作的一个组成部分。长寿命，电荷分离状态是实现光伏和光催化组件的关键。这项研究的动机是需要了解分子重组和金属自旋态在控制电荷分离态寿命和催化选择性/效率中的作用。这项研究建立在他们最近探索电荷转移诱导的自旋交叉化合物以及伴随的分子重组对光诱导电子转移过程的影响的基础上。从所提出的研究中收集的结果将使光诱导反应性中自旋和重组能的结构-功能关系的发展成为可能，迄今为止，这些关系还相对未被探索。他们的目标是回答以下问题：高自旋/低自旋电子状态跃迁对光诱导电荷分离寿命的作用是什么？在前一个目标中揭示的设计原则是否可以扩展到更严重的分子重组，即分子间和分子内配体结合/解离？分子自旋状态是否控制光催化机制，即速率和路径？该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

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.