Electronic Distance Effects, Temperature Effects and External Orbital Effects in Optical Hole (and Electron) Transfer Reactions

光空穴（和电子）转移反应中的电子距离效应、温度效应和外轨道效应

• 批准号: 8921590
• 负责人: Joseph Hupp
• 金额: $ 17.41万
• 依托单位: Northwestern University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-05-15 至 1993-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8921590&HistoricalAwards=false
• 关键词: Electronic; Distance; Effects; Temperature; External

With this award from the Inorganic, Bioinorganic and Organometallic Chemistry Program Dr. Joseph T. Hupp will assess the various factors which govern the light-induced transfer of electrons between the metal centers in molecules which contain two metal atoms. The information to be gained will provide a deeper understanding of processes which are important in the conversion of light energy to chemical energy and in biological electron transfer. The goal of the project is to assess directly various superexchange contributions to intervalence charge-transfer reactions in bimetallic complexes. The modulation of electronic interactions by changes in distance, temperature, solvent and external orbitals will be investigated. The experimental strategy will involve the synthesis of a variety of new polypyridyl ligands designed to modulate the distance of separation of the two metals, and of a variety of new bifunctional crown ether-containing ligands designed to modulate intervalence charge transfer by forming inclusion complexes with either aromatic molecules or with simple closed-shell cations.

获得无机、生物无机和有机金属化学项目的奖项后，约瑟夫·t·赫普博士将评估控制包含两个金属原子的分子中金属中心之间光诱导电子转移的各种因素。所获得的信息将使我们对光能转化为化学能和生物电子转移的重要过程有更深入的了解。该项目的目标是直接评估各种超交换对双金属配合物中价间电荷转移反应的贡献。通过距离、温度、溶剂和外轨道的变化对电子相互作用的调制将被研究。实验策略将包括合成各种新的聚吡啶配体，以调节两种金属的分离距离，以及各种新的双功能冠醚配体，通过与芳香分子或简单的闭壳阳离子形成包合物来调节价间电荷转移。