Charge Transfer Across Organic Bridges

这项来自有机动力学项目的资助支持了这项工作 Stuart W教授卡耐基梅隆大学。 双环辛四烯二阴离子的动力学过程将是 通过核磁共振光谱检查。 的 键转移和电荷转移的活化势垒将 通过完整的线形分析、饱和度 转移或通过其他NMR方法。 的区别 这些值将等同于“纯”电荷转移 没有任何重大的构象变化。 这些电荷 传输速率与电子耦合有关， 溶剂分离离子配对和阳离子转移条件 在接触离子配对的条件下。 费率将是 作为桥连基团的特性的函数测量， 阳离子和溶剂。 %%% 含两个环的化合物中的电子转移 将检查由间隔基团分开的环。 这些 研究将在以下条件下进行： 带正电荷的物质（阳离子） 与富电子环相关的 的速率 电子转移作为连接的间隔基团的函数， 两个戒指将提供关于 间隔物用作电子转移的导管。 的 溶剂对电子转移的影响也将是 考察

This grant from the Organic Dynamics Program supports the work of Professor Stuart W. Staley at Carnegie Mellon University. Dynamic processes in bicyclooctatetraenyl dianions will be examined by nuclear magnetic resonance spectroscopy. The activation barriers for bond shifting and charge transfer will be determined by complete line shape analysis, saturation transfer, or by other NMR methods. The difference between these values will be equated to "pure" charge transfer in the absence of any major conformational change. These charge transfer rates are related to electronic coupling under conditions of solvent-separated ion pairing and cation transfer under conditions of contact ion pairing. The rates will be measured as functions of the identities of the bridging group, cation, and solvent. %%% Electron transfer from ring to ring in compounds containing two rings separated by spacer groups will be examined. These studies will be conducted under conditions in which a positively charged species (a cation) is and is not tightly associated with the electron-rich ring. The rate at which the electrons transfer as a function of spacer group connecting the two rings will provide valuable information on the ability of the spacer to act as a conduit for electron transfer. The effect of solvent on the electron transfer will also be examined.