Photochemistry of Metal Complexes

在化学部无机、生物无机和有机金属计划的这一项目中，加州理工学院的哈里·B·格雷博士将对Ir核和通过刚性间隔物连接到核上的吡啶受体之间的远程电子转移进行系统研究。间隔器将由饱和和不饱和碳单元建造。预计这项工作将产生基本信息，这些信息将有助于开发太阳能转换和信息存储的分子方法。通过各种刚性间隔物的电子转移速率的广泛测量将能够确定电子耦合与间隔物长度和电子结构之间的关系。Ir核由Ir(I)二聚体组成，作为电子供体。受体是与所选分子中亚膦配体结合的N-烷基吡啶基团。Ir原子通过3，5-二甲基吡唑基桥联，也与羰基配体结合。这种分子含有一个明显的反转区域，因此可以研究单态和三态金属到配体的电子转移和热配体到金属的反向转移。这些结果将会引起不同领域的化学家的兴趣，包括光谱学、表面催化和金属蛋白的表征。

In this project in the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division, Dr. Harry B. Gray of California Institute of Technology will conduct systematic studies on long-range electron transfer between an iridium core and pyridinium acceptors connected to the core by rigid spacers. The spacers will be built from both saturated and unsaturated carbon units. The work is expected to yield fundamental information that will be helpful in developing molecular approaches to solar energy conversion and information storage. Extensive measurements of electron transfer rates through various rigid spacers will enable the relationships betweenelectronic coupling and spacer length and electronic structure to be determined. The iridium core consists of an Iridium (I) dimer, which serves as the electron donor. The acceptors are N-alkylpyridinium groups bound to phosphinite ligands in the molecule selected for study. The iridium atoms are bridged by 3,5-dimethylpyrazolyl and are also bound to carbonyl ligands. This molecule contains a pronounced inverted region so that singlet and triplet metal to ligand electron transfer and thermal ligand to metal back transfer can be investigated. The results will be of interest to chemists in a variety of fields, including spectroscopy, surface catalysis, and chacterization of metalloproteins.