Electron Transfer Photochemistry

在化学系有机动力学项目的支持下，新墨西哥大学化学系的Mariano教授将专注于由激发态单电子转移（SET）引发的新型光化学反应的发展和机理理解，这些反应通过短寿命自由基离子的中介发生。在这些研究中采用的方法是基于机械的，因此，结果应该有助于理解离子自由基化学和控制set促进光化学反应的性质和效率的因素。此外，set促进的光化学反应将发展成为制备生物医学领域潜在重要有机物质的实用方法。这方面的一个例子是在生物学上重要的有丝新世骨架的制备中提出的高度简明的方法。虽然这些研究集中在set -光化学过程，但它们更广泛地用于解决与现代有机化学的几个子领域有关的根本性重要问题。例如，从受体-多供体体系中获得的两性离子双自由基中控制链内SET速率的因素，以及控制这些物质的区域选择性和SET促进反应效率的因素，这些知识与有机电化学领域高度相关，并且可能与新导电材料的设计密切相关。在化学学部有机动力学项目的支持下，Mariano教授对set促进的受体-多供体系统的光环化反应的研究将导致新的和有效的方法的发展，以制备有趣的大环化合物，可以作为有效的分子识别和离子传感剂。最后，拟议的研究将对化学教育产生重大影响，因为它们将作为合成和物理有机化学领域博士生广泛和全面教育的基础。

With the support of the Organic Dynamics Program in the Chemistry Division, Professor Mariano, of the Chemistry Department at the University of New Mexico, will focus on the development and mechanistic understanding of new photochemical reactions that are initiated by excited state single electron transfer (SET) and take place through the intermediacy of short-lived radical ions. The approaches taken in these studies are mechanistically grounded and, consequently, the results should contribute significantly to the understanding of ion radical chemistry and the factors that govern the nature and efficiencies of SET-promoted photochemical reactions. Furthermore, the SET-promoted photochemical reactions will be developed as practical methods for the preparation of organic substances of potential importance in biomedical areas. An example of this is found in the highly concise approach proposed for preparation of the biologically important mitocene skeleton. Although the investigations concentrate on SET-photochemical processes, they are more broadly designed to address fundamentally important questions that relate to several sub-areas of modern organic chemistry. For example, knowledge gained about the factors that govern the rates of intra-chain SET in zwitterionic biradicals derived from acceptor-polydonor systems and that control the regioselectivities and efficiencies of SET-promoted reactions of these substances are highly relevant to the areas of organic electrochemistry, and potentially, the design of new conductive materials.With the support of the Organic Dynamics Program in the Chemistry Division, Professor Mariano's studies of SET-promoted photocyclization reactions of acceptor-polydonor systems will lead to the development of new and efficient methods to prepare interesting macrocyclic compounds that could serve as effective molecular recognition and ion sensing agents. Finally, the proposed studies will have a significant impact on chemical education since they will serve as a foundation for the broad and comprehensive education of doctoral students in the areas of synthetic and physical organic chemistry.