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

在获得无机化学、生物无机化学和金属有机化学项目的这一奖项后，Joseph T.Hupp博士将评估控制包含两个金属原子的分子中的金属中心之间的光诱导电子转移的各种因素。将获得的信息将使人们更深入地了解在将光能转化为化学能和生物电子转移中至关重要的过程。该项目的目标是直接评估各种超交换对双金属络合物中价间电荷转移反应的贡献。我们将研究距离、温度、溶剂和外轨道的变化对电子相互作用的影响。实验策略将包括合成各种新的多吡啶配体，旨在调节两种金属的分离距离，以及各种新的双功能冠醚配体，旨在通过与芳香族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。

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.