Photochemistry of Metal Complexes

在化学学部无机、生物无机和有机金属项目的这个项目中，加州理工学院的Harry B. Gray博士将对铱核和通过刚性间隔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。隔离剂将由饱和和不饱和碳单元构成。这项工作有望产生基本信息，这将有助于开发太阳能转换和信息存储的分子方法。通过各种刚性间隔的电子传输速率的广泛测量将使电子耦合和间隔长度和电子结构之间的关系得以确定。铱核由铱(I)二聚体组成，它充当电子供体。受体是n -烷基吡啶基团，与分子中的亚磷酸盐配体结合。铱原子由3,5-二甲基吡唑基桥接，也与羰基配体结合。该分子包含一个明显的反转区，因此可以研究单线态和三重态金属到配体的电子转移和热配体到金属的背转移。这些结果将引起许多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.