Photoreaction and Photophysical Mechanisms of Transition Metal Complexes

无机、生物无机与有机化学 该计划支持基础光化学的研究， 过渡金属有机化合物和配位化合物。 的 本建议中所述的关于 自旋平衡络合物对该领域具有实际意义 光信息存储的研究，以及 和表征活性有机金属中间体 对催化和表面化学具有实际重要性。 建议研究基础化学和 控制反应的物理机制和其他 激发态和反应态的失活过程 由过渡金属的光激发形成的中间体 有机金属和配位化合物。 一个主要重点是 放置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暂的 物种，并定量研究它们的反应动力学， 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制度 包括1）铜（I）的强发光配合物， 铂（II）和铑（III）; 2）铁（II）化合物， 五重态/单重态自旋平衡和3）催化活性 铑和铱加某些金属的膦络合物 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.