Photochemical and Electrochemical Reactions of Organometallic Molecules

在流体溶液中，在刚性基质中，以及附着在表面上的分子种类将被考虑，其总体目标和意义是电子结构和反应性的相关性，以及建立光和电化学诱导反应发生的详细途径。在电子开关器件、微电子、半导体及相关电子材料中有潜在的应用。提出了有机金属分子在流体溶液、刚性介质和表面上的光化学和电化学研究。研究的目的是了解与金属配合物的电子构型变化有关的化学和物理后果。此外，为了更好地理解光反应和氧化还原过程的机制，将对光化学和电化学生成的中间体进行化学和光谱表征。要研究的具体体系包括金属-金属键配合物，以确定影响光取代反应活性的因素和配位不饱和金属-金属键体系的反应活性。另一类要研究的分子是单核系统，以建立化学计量和催化反应的机制。该方法包括利用光在低温下产生配位不饱和物质，然后进行预热实验以影响热反应。该研究的剩余重点涉及氧化还原聚合物的合成，以说明结合的有机金属亚基的反应性可以通过电化学手段进行调节。

Molecular species in fluid solution, in rigid matrices, and attached to surfaces are to be considered with the overall objectives and significance being the correlation of electronic structure and reactivity and in establishing the detailed pathway by which light- and electrochemically-induced reactions occur. There are potential applications in electronic switching devices, microelectronics, semiconductors and related electronic materials. Photochemical and electrochemical studies of organometallic molecules in fluid solution, in rigid media, and on surfaces are proposed. The objective of the research is to understand chemical and physical consequences associated with changes in the electron configuration of the metal complex. Additionally, chemical and spectroscopic characterization of photochemically and electrochemically generated intermediates will be carried out in order to better understand mechanisms of photoreactions and redox processes. Specific systems to be investigated include metal-metal bonded complexes to determine factors influencing photosubstitution reactivity and the reactivity of coordinatively unsaturated metal-metal bonded systems. Another class of molecules to be investigated are mononuclear systems to establish aspects of the mechanism of stoichiometric and catalytic reactions. The approach involves using light to generate coordinatively unsaturated species at low temperature followed by warm up experiments to effect thermal reactions. The remaining thrust of the research involves synthesis of redox polymers to illustrate that reactivity of bound organometallic subunits can be tuned by electrochemical means.