Photochemical and Photophysical Mechanisms of Transition Metal Complexes

该奖项授予无机化学、生物无机化学和金属有机化学项目，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持续支持。工作将集中在两类化合物：金属亚硝酰和亚硝酸络合物，以及多核铜(I)络合物。第一个项目的目标是阐明一氧化氮(NO)产生的光化学机制，以及NO与生物无机感兴趣的金属中心反应的动力学。将对各种单核金属亚硝酰基和金属亚硝酸络合物进行闪光和连续光解，特别强调可作为按需将NO光化学输送到所需目标的前体的化合物。此外，还将研究可作为检测NO的发光传感器的双生色团体系的合成及其光化学-光物理表征。第二个项目将研究含有d-10金属中心的单核和簇合物的光致发光行为，主要是铜(I)，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被用于启动化学反应，有时被重新发射为不同波长的光(发光)。这项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，在特定靶点受控释放NO可带来医疗益处。这项研究将有助于理解NO与生物分子的相互作用以及监测其影响的能力。研究金属团簇激发态性质的变化关系到光光学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.