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

CAS：利用光诱导化学中的自旋：长寿命电荷分离态和氧化催化中高自旋和低自旋过渡金属的基础探索

• 批准号: 2153862
• 负责人: Amanda Morris
• 金额: $ 52.5万
• 依托单位: Virginia Polytechnic Institute and State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-05-01 至 2025-04-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2153862&HistoricalAwards=false
• 关键词: CAS; Exploiting; Spin; Photo; induced

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.

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，弗吉尼亚理工学院暨州立大学化学系的Amanda Morris和Gordon Yee教授正在探索分子自旋态在光化学工作中的作用。对分子-金属氧化物界面的分子重组和自旋的系统研究，有可能影响光催化、光伏和量子信息科学等各种应用领域的研究领域。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 和大学水平的教育丰富化提供了广泛的基础，包括促进科学多样性的努力，将成为资助工作的一部分。电荷分离态对于光伏和光催化组件的实现至关重要，该研究的动机是了解分子重组和金属自旋态在控制中的作用。该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。将能够发展光诱导反应中自旋和重组能的结构-功能关系，迄今为止，这些关系尚未得到探索。他们的目标是回答以下问题：光致电荷分离寿命中的高自旋/低自旋电子态转变是否可以扩展到更严格的分子重组，即分子间和分子内配体缔合/解离？光催化机制，即速率和路径？该奖项反映了 NSF 的法定使命，并通过使用基金会的智力优点和更广泛的影响审查标准进行评估，被认为值得支持。