Photoinduced Electron and Energy Transfer in Molecular Assemblies

这个无机、生物无机和有机金属化学项目的奖项支持北卡罗来纳大学教堂山分校化学系的Thomas J. Meyer博士对电子转移反应的研究。为了更好地理解光致电子和能量转移的一般现象，我们将研究分子组装中多吡啶配合物的金属到配体的电荷转移（MLCT）激发态。将合成发色团猝灭剂和配体桥接组合。这些新的组件将被设计用于以下研究：(a)新的光物理现象，特别是在马库斯倒转区域，包括分子内竞争、时间延迟和多光子效应；(b)基于不对称取代联吡啶配体的顺/反异构的新结构基序的作用；(c)通过使用桥接电子转移配体长时间储存光化学氧化还原等价物；(d)光化学能转换。光谱参数将用于计算电子转移速率常数。研究大分子的电子性质和分子间的结合，最终目的是开发分子级电子器件。本研究涉及基于颜色变化的光化学能量转换和信息存储。为了发展这项技术，必须更好地理解电子在长距离和长时间尺度上的运动。

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research on electron transfer reactions by Dr. Thomas J. Meyer of the Chemistry Department, University of North Carolina at Chapel Hill. Metal-to-ligand charge transfer (MLCT) excited states of polypyridyl complexes in molecular assemblies will be studied in order to better understand the general phenomenon of photoinduced electron and energy transfer. Chromophore-quencher and ligand-bridged assemblies will be synthesized. These new assemblies will be designed for the investigation of the following: (a) novel photophysical phenomena particularly in the Marcus inverted region, including intramolecular competition, time delays, and multi-photon effects; (b) the role of new structural motifs, based on cis/trans isomerism at unsymmetrically substituted bipyridine ligands; (c) long-lived storage of photochemical redox equivalents through the use of bridging electron transfer ligands; and (d) photchemical energy conversion. Spectroscopic parameters will be used to calculate electron transfer rate constants. Investigation of the electronic properties of large molecules and associations of molecules, or assemblies, is ultimately aimed at development of molecular-level electronic devices. This research is relevant to photochemical energy conversion and information storage based on color changes. To develop this technology, movement of electrons over long distances and over long time scales must be better understood.