CAS: Proton-Coupled Electron Transfer Reactions from Ligand-to-Metal Charge Transfer Excited States.

CAS：配体到金属电荷转移激发态的质子耦合电子转移反应。

• 批准号: 2400727
• 负责人: Jillian Dempsey
• 金额: $ 55万
• 依托单位: University of North Carolina at Chapel Hill
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2024
• 资助国家: 美国
• 起止时间: 2024-08-01 至 2027-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2400727&HistoricalAwards=false
• 关键词: CAS; Proton; Coupled; Electron; Transfer

WIth support from the Chemical Structure, Dynamics & Mechanisms-B (CSDM-B) Program of the Chemistry Division, Professor Jillian Dempsey of the Department of Chemistry at University of North Carolina at Chapel Hill is studying new strategies for driving fuel and chemical production with light. The goal of the project is to establish light-activated reactions that form transition metal hydride complexes. Many of the catalytic processes by which fuels and commodity chemicals are produced proceed through transition metal hydride complexes. Therefore, routes to synthesize transition metal hydrides with light provide a sustainable route for fuel and chemical synthesis. The research activities will contribute to the development of a globally competitive science and technology workforce as trainees will develop skills in chemical synthesis and spectroscopy. Complementary activities led by Professor Dempsey aim to broaden participation of historically marginalized communities in science and to train a globally competitive workforce. Professor Dempsey leads the Chemistry Women Mentorship Network, which connects graduate students and postdoc women interested in academic careers with faculty mentors and designs resources to support successful mentor-mentee relationships. Professor Dempsey also leads a three-day workshop that provides hands-on training in both theoretical and practical aspects of electrochemistry to researchers around the country. The generation of transition metal hydride complexes using light would enable approaches that employ solar energy to drive these important, energy-intensive reactions. The excited-state proton-coupled electron transfer reactivity of transition metal complexes with ligand-to-metal charge transfer excited states has not yet been established, but is a promising strategy for integrating light capture and proton-electron reactivity. Under this award, foundational studies of coordination complexes with ligand-to-metal charge transfer excited states that combine synthesis, spectroscopy, and theory will be undertaken to establish the electronic structure factors necessary for low energy ligand-to-metal charge transfer transitions. Subsequently, photochemistry accessible from ligand-to-metal charge transfer excited states will be investigated, with a focus on demonstrating the scope of excited-state electron and proton transfer reactions accessible. Structure-function relationships and time-resolved spectroscopy will be instrumental in gaining new insight to photochemistry from these excited states. This knowledge will guide the investigation of unprecedented proton-coupled electron transfer reactions from complexes with ligand-to-metal charge transfer excited states. Spectroscopy and theory will provide key insight to the electronic structure properties that engender proton-coupled electron transfer reactivity. If successful, these studies will establish new strategies for integrating light capture and proton-electron reactivity.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.

在化学系化学结构、动力学和机理-B (CSDM-B) 项目的支持下，北卡罗来纳大学教堂山分校化学系的 Jillian Dempsey 教授正在研究推动燃料和化学品生产的新策略光。该项目的目标是建立形成过渡金属氢化物络合物的光激活反应。生产燃料和商品化学品的许多催化过程都是通过过渡金属氢化物络合物进行的。因此，利用光合成过渡金属氢化物的路线为燃料和化学合成提供了可持续的路线。研究活动将有助于培养具有全球竞争力的科学和技术劳动力，因为学员将培养化学合成和光谱学方面的技能。登普西教授领导的补充活动旨在扩大历史上边缘化社区对科学的参与，并培训一支具有全球竞争力的劳动力队伍。登普西教授领导着化学女性导师网络，该网络将对学术职业感兴趣的研究生和博士后女性与教师导师联系起来，并设计资源以支持成功的导师与学员关系。登普西教授还主持了一个为期三天的研讨会，为全国各地的研究人员提供电化学理论和实践方面的实践培训。利用光生成过渡金属氢化物络合物将使利用太阳能来驱动这些重要的能源密集型反应成为可能。具有配体到金属电荷转移激发态的过渡金属配合物的激发态质子耦合电子转移反应性尚未建立，但它是整合光捕获和质子电子反应性的一种有前途的策略。在该奖项下，将结合合成、光谱学和理论，对具有配体到金属电荷转移激发态的配位配合物进行基础研究，以确定低能配体到金属电荷转移跃迁所需的电子结构因素。随后，将研究配体到金属电荷转移激发态的光化学，重点是展示激发态电子和质子转移反应的范围。结构-功能关系和时间分辨光谱将有助于从这些激发态获得光化学的新见解。这些知识将指导对具有配体到金属电荷转移激发态的络合物的前所未有的质子耦合电子转移反应的研究。光谱学和理论将为产生质子耦合电子转移反应性的电子结构特性提供关键见解。 如果成功，这些研究将建立整合光捕获和质子电子反应性的新策略。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。