Photoreaction and Photophysical Mechanisms of Transition Metal Complexes

无机、生物无机和有机金属化学项目支持过渡金属、有机金属和配位化合物的基础光化学研究。本文对自旋平衡配合物弛豫动力学的研究与光学信息存储领域具有实际意义，对活性有机金属中间体的检测和表征工作对催化和表面化学具有实际意义。本文旨在研究过渡金属有机化合物和配位化合物光激发形成的激发态和活性中间体的反应和其他失活过程的基本化学和物理机制。主要的重点放在使用闪光灯和激光脉冲光解与时间分辨发光和瞬态吸收光谱技术来制备和表征这些短寿命的物种，并定量研究它们的反应动力学作为反应介质的性质和条件的函数。作为这些持续研究的一部分提出的具体系统包括：1)铜(I)、铂（II）和铑（III）的强发光配合物；2)铁（II）化合物显示五重/单重态自旋平衡；3)铑和铱的催化活性磷配合物加上某些金属羰基簇。

The Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research in the fundamental photochemistry of transition metal organometallic and coordination compounds. The studies described in this proposal on relaxation dynamics of spin equilibrium complexes have practical relevance to the field of optical information storage, and the work on detecting and characterizing reactive organometallic intermediates has practical importance to catalysis and surface chemistry. It is proposed to investigate the fundamental chemical and physical mechanisms governing the reactions and other deactivation processes of excited states and reactive intermediates formed by the photoexcitation of transition metal organometallic and coordination compounds. A major emphasis is placed on the use of flash lamp and laser pulse photolysis with time resolved luminescence and transient absorption spectral techniques to prepare and to characterize these short-lived species and to study quantitatively their reaction dynamics as functions of the nature and condition of the reaction medium. Specific systems proposed as part of these continuing studies include 1) strongly luminescent complexes of copper(I), platinum(II) and rhodium(III); 2) iron(II) compounds displaying quintet/singlet spin equilibria and 3) catalytically active phosphine complexes of rhodium and iridium plus certain metal carbonyl clusters.