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.

在化学部的化学结构，动力学和机制-B（CSDM-B）计划的支持下，北卡罗来纳大学教堂山化学系的吉利安·登普西教授正在研究新的策略，以用光来驱动燃料和化学生产。该项目的目的是建立形成过渡金属氢化物络合物的光激活反应。通过过渡金属氢化物络合物进行燃料和商品化学物质的许多催化过程。因此，用光合成过渡金属氢化物的途径为燃料和化学合成提供了可持续的途径。研究活动将有助于发展全球竞争性的科学和技术劳动力，因为受训者将发展化学合成和光谱学的技能。 Dempsey教授领导的互补活动旨在扩大历史上边缘化的科学社区的参与并培训全球竞争激烈的劳动力。 Dempsey教授领导化学女性指导网络，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关系。 Dempsey教授还主持了为期三天的研讨会，该研讨会在全国研究人员的理论和实践方面提供了动手培训。使用光的过渡金属氢化物复合物的产生将实现采用太阳能驱动这些重要的，能源密集型反应的方法。尚未确定具有配体到金属电荷转移态的激发质质子耦合的电子转移反应性激发态尚未建立，但是整合光捕获和质子电子反应性的有希望的策略。根据该奖项，将对合成，光谱和理论结合的配体与金属电荷转移状态进行协调复合物的基础研究，以确定低能配体与金属电荷转移过渡所必需的电子结构因子。随后，将研究可从配体到金属电荷转移激发态访问的光化学，重点是证明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学将有助于从这些激发态中获得对光化学的新见解。这些知识将指导从具有配体到金属电荷转移激发态的复合物的前所未有的质子偶联电子转移反应的研究。光谱和理论将为导致质子耦合电子转移反应性的电子结构特性提供关键见解。 如果成功的话，这些研究将建立新的策略，以整合光捕获和质子 - 电子的反应性。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子优点和更广泛的影响审查标准通过评估来支持的。