Photochemical and Photophysical Mechanisms of Transition Metal Complexes

这个无机、生物无机和有机金属化学项目的奖项为加州大学圣巴巴拉分校化学系Peter C. Ford博士的光化学研究提供了持续的支持。工作将集中在两类化合物：金属亚硝基和亚硝基配合物，以及多核铜(I)配合物。第一个项目的目标是阐明一氧化氮（NO）生成的光化学机制以及NO与生物无机感兴趣的金属中心反应的动力学。将进行各种单核金属亚硝基和金属亚硝基配合物的快速和连续光解，特别强调可能作为光化学将NO传递到所需目标的前体的化合物。此外，还将研究可作为NO检测光传感器的双发色团体系的合成及其光化学-光物理特性。第二个项目将研究含有d-10金属中心（主要是铜）的单核和团簇化合物的光致发光行为，包括激发态性质如何响应介质性质的扰动。当光被分子吸收时，分子获得的能量有时用于引发化学反应，有时作为不同波长的光（发光）重新发射。本研究中使用的方法可以确定这两种类型的变化。一氧化氮（NO）影响生物调节和免疫反应，在特定靶点上控制NO的释放可获得医疗效益。本研究将有助于了解一氧化氮与生物分子的相互作用及其监测其作用的能力。研究金属团簇激发态性质的变化关系到光器件和光催化剂的设计、优化和应用。

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program provides continued support for photochemical research by Dr. Peter C. Ford, Chemistry Department, University of California, Santa Barbara. Work will focus on two classes of compounds: metal nitrosyl and nitrito complexes, and polynuclear copper(I) complexes. The goal of the first project is to elucidate the photochemical mechanisms of nitric oxide (NO) generation as well as the dynamics of NO reactions with metal centers of bioinorganic interest. Flash and continuous photolysis of various mononuclear metal nitrosyl and metal nitrito complexes will be conducted, placing particular emphasis on compounds that may serve as precursors for the photochemical delivery of NO to desired targets on demand. In addition, the synthesis and photochemical-photophysical characterization of dual chromophore systems that might serve as luminactive sensors for detection of NO will be studied. The second project will investigate the photoluminescent behavior of mononuclear and cluster compounds containing d-10 metal centers, primarily copper(I), including how the excited state properties respond to perturbations in the properties of the media. When light is absorbed by a molecule, the energy that the molecule acquires is sometimes used to initiate a chemical reaction and sometimes is re-emitted as light of a different wavelength (luminescence). The methods used in this study enable changes of both types to be determined. Nitric oxide(NO) affects bioregulatory and immune response and medical benefits could be derived from controlled release of NO at specific targets. This study will contribute to the understanding of the interaction of NO with biomolecules and the ability to monitor its effects. Studies of the changes of excited state properties of metal clusters are relevant to the design, optimization, and application of photooptical devices and photocatalysts.