CAREER: Earth-Abundant Transition Metal Photosensitizers Using Ligand-to-Metal Charge Transfer

职业：利用配体到金属电荷转移的地球丰富的过渡金属光敏剂

• 批准号: 1752738
• 负责人: Carsten Milsmann
• 金额: $ 64.94万
• 依托单位: West Virginia University Research Corporation
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-05-01 至 2024-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1752738&HistoricalAwards=false
• 关键词: CAREER; Earth; Abundant; Transition; Metal

In this CAREER project, funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Carsten Milsmann of the Department of Chemistry at West Virginia University is investigating a new class of early transition metal complexes that are promising candidates for the development of molecular photosensitizers due to their interesting optical and electrochemical characteristics. Molecular photosensitizers find application in a wide variety of solar energy applications including photovoltaics, solar fuel production, and photocatalysis. The goal of these research efforts is to provide access to photoactive compounds based on readily-available, earth-abundant metals that can improve upon and/or replace currently available technology based on precious metals. This will further the development of more cost-efficient solar energy applications for which scalability is not hindered by the limited availability of the metal component. The project requires expertise in the fields of inorganic, physical, and organic chemistry and is ideally suited for the training and education of highly qualified scientists at all levels. Outreach activities aimed at middle school students in rural areas of West Virginia will be conducted in collaboration with the West Virginia University Center for Excellence in Science Education and support efforts to train the next generation of science teachers in the state.The electron-deficient nature of early transition metals requires new approaches to initial charge separation via absorption of a photon compared to the well-established functional principles of electron-rich precious metal photosensitizers. This project investigates ligand-to-metal charge transfer processes to convert light energy into chemical potentials. Through a combination of synthetic chemistry, spectroscopic studies, and quantum-chemical calculations this project are answering the following questions: 1)What are the fundamental design principles to generate long-lived excited states in early transition metal complexes? 2)How can systematic modifications of the supporting ligand framework be used to fine-tune the optical and electron transfer properties of the complexes? 3)Can the photo-induced electron transfer properties of early transition metal complexes be utilized to enable transformations requiring highly reducing conditions (e.g. dinitrogen reduction)?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、动力学和机理 B 项目资助的职业项目中，西弗吉尼亚大学化学系的 Carsten Milsmann 教授正在研究一类新型早期过渡金属配合物，由于其有趣的光学和电化学特性，这些配合物是开发分子光敏剂的有希望的候选者。分子光敏剂可广泛应用于各种太阳能应用，包括光伏、太阳能燃料生产和光催化。 这些研究工作的目标是提供基于容易获得的、地球丰富的金属的光活性化合物，这些化合物可以改进和/或取代目前基于贵金属的技术。这将进一步开发更具成本效益的太阳能应用，其可扩展性不会因金属组件的有限可用性而受到阻碍。该项目需要无机、物理和有机化学领域的专业知识，非常适合各级高素质科学家的培训和教育。针对西弗吉尼亚州农村地区中学生的外展活动将与西弗吉尼亚大学科学教育卓越中心合作开展，并支持培训该州下一代科学教师的努力。与富电子贵金属光敏剂的完善功能原理相比，早期过渡金属的缺电子性质需要通过吸收光子来实现初始电荷分离的新方法。该项目研究配体到金属的电荷转移过程，将光能转化为化学势。通过合成化学、光谱研究和量子化学计算的结合，该项目回答了以下问题：1）在早期过渡金属配合物中产生长寿命激发态的基本设计原则是什么？ 2）如何通过支持配体框架的系统修饰来微调配合物的光学和电子转移特性？ 3）能否利用早期过渡金属配合物的光诱导电子转移特性来实现需要高度还原条件（例如二氮还原）的转化？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。

项目成果

Effects of Ligand Substitution on the Optical and Electrochemical Properties of (Pyridinedipyrrolide)zirconium Photosensitizers

配体取代对(吡啶二吡咯)锆光敏剂光学和电化学性质的影响

• DOI: 10.1021/acs.inorgchem.0c02343
• 发表时间: 2020
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Zhang, Yu;Leary, Dylan C.;Belldina, Anne M.;Petersen, Jeffrey L.;Milsmann, Carsten
• 通讯作者: Milsmann, Carsten

Photochemical C–C Bond Formation in Luminescent Zirconium Complexes with CNN Pincer Ligands

• DOI: 10.1021/acs.organomet.8b00388
• 发表时间: 2018-08
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Yu Zhang;J. L. Petersen;Carsten Milsmann

Photochemical synthesis of a zirconium cyclobutadienyl complex

• DOI: 10.1039/d0cc01104e
• 发表时间: 2020-05-18
• 期刊: CHEMICAL COMMUNICATIONS
• 影响因子: 4.9
• 作者: Do, P. Minh N.;Akhmedov, Novruz G.;Milsmann, Carsten
• 通讯作者: Milsmann, Carsten

Delayed fluorescence from a zirconium(iv) photosensitizer with ligand-to-metal charge-transfer excited states

• DOI: 10.1038/s41557-020-0430-7
• 发表时间: 2020-03
• 期刊: Nature Chemistry
• 影响因子: 21.8
• 作者: Yu Zhang;Tia S. Lee;Joseph M. Favale;Dylan C. Leary;J. L. Petersen;G. Scholes;F. Castellano;Carsten Milsmann

Long-Lived Photoluminescence of Molecular Group 14 Compounds through Thermally Activated Delayed Fluorescence

• DOI: 10.1021/acs.inorgchem.2c00182
• 发表时间: 2022-05-16
• 期刊: INORGANIC CHEMISTRY
• 影响因子: 4.6
• 作者: Gowda, Anitha S.;Lee, Tia S.;Milsmann, Carsten
• 通讯作者: Milsmann, Carsten