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.

在这个职业项目中，由化学结构，动态和机制B计划资助，西弗吉尼亚大学化学系的Carsten Milsmann教授正在调查一类新的早期过渡金属复合物，这些综合物是由于其有趣的光学和电化学特征而导致的分子光吸收器的有希望的候选者。分子光敏剂在多种太阳能应用中发现了应用，包括光伏，太阳能燃料的产生和光催化。 这些研究工作的目的是基于易于获得的，丰富的金属的光活性化合物，可以根据贵金属改进和/或替换当前可用的技术。这将进一步开发更具成本效益的太阳能应用，而金属组件的可用性有限地阻碍了可伸缩性。该项目需要在无机，物理和有机化学领域的专业知识，非常适合对各个级别的高素质科学家的培训和教育。将与西弗吉尼亚大学科学教育卓越和支持努力进行培训该州的下一代科学教师的卓越努力的外展活动将与培训该州的下一代科学教师合作进行。早期过渡金属的电子缺陷性质需要新的方法来通过吸收良好的功能级的珍贵的电子产品来吸收初始收费，以通过吸收来源。该项目调查了配体到金属电荷转移过程，以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）在早期过渡金属复合物中产生长期持久激发态的基本设计原理是什么？ 2）如何使用支撑配体框架的系统修饰来微调复合物的光学和电子传递特性？ 3）是否可以利用光诱导的电子转移金属复合物的电子传递性能来实现需要高度降低条件的转换（例如，减少二氮）？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和更广泛影响的审查标准来通过评估来通过评估来支持的。

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

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

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