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.

在这个由化学系化学结构、动力学机制B计划资助的项目中，弗吉尼亚理工学院和州立大学化学系的阿曼达·莫里斯教授和戈登·易教授正在探索分子自旋态在光化学中的作用。拟议的工作构成了对分子-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空间的研究领域，包括量子化学，光子学和量子信息科学。跨学科项目汇集了分子无机，材料和物理化学的知识，为K-12和大学水平的教育丰富提供了广泛的基础。推广，包括努力促进科学的多样性，将是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。提出的研究的动机是需要了解分子重组和金属自旋状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的工作，探索电荷转移诱导的自旋交叉化合物和伴随的分子重组对光诱导电子转移过程的影响。从拟议的研究中收集的结果将使相对于自旋和重组能量的光诱导反应，到目前为止，已经相对未开发的结构-功能关系的发展。 他们的目标是回答以下问题：高自旋/低自旋电子态跃迁对光诱导电荷分离寿命的作用是什么？在前面的目标中发现的设计原理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缔合/解离？分子自旋状态控制光催化机制，即，速度和路径？该奖项反映了NSF的法定使命，并被认为是值得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的支持。