Linked Donor/Acceptor/Photosensitizer Systems

该项目属于分析和表面化学的一般领域，以及光化学和电化学的子领域。化学合成方法将被用来制备各种各样的连接分子内电子转移系统，这些系统具有非连接系统所没有的独特性质。这些配合物是基于三联吡啶(II)作为捕光中心的。该光中心通过柔性键连接到N，N‘-二季铵-2，2’-联吡啶作为电子受体和/或N-烷基吩噻嗪作为电子供体。在其他系列中，将研究具有相对刚性键的三桥异双核Ru/Rh配合物。基态性质将通过电化学、光谱电化学和光谱方法进行表征。电子转移速率将通过时间分辨发射光谱和吸收光谱来确定。电化学、光化学和光物理相结合的研究将有助于更好地理解光诱导电子转移体系的分子水平。这些结果将有助于设计更有效的分子系统，将光能转化为有用的化学能。

This project is in the general field of analytical and surface chemistry and in the subfields of photochemistry and electrochemistry. Chemical synthetic methods will be employed to prepare a wide variety of linked intramolecular electron transfer systems that have unique properties absent in non-linked systems. The complexes are based on trisbipyridine (II) as a light-harvesting photocenter. This photocenter is covalently linked via flexible linkages to N,N'-diquaternary- 2,2'-bipyridinium as an electron acceptor and/or N-alkyl phenothiazine as an electron donor. In other series, triply bridged heterodinuclear ruthenium/rhodium complexes with relatively rigid linkages will be studied. Ground state properties will be characterized by electrochemical, spectroelectrochemical and spectroscopic methods. Electron transfer rates will be determined by time-resolved emission and absorption spectroscopy. Combined electrochemical, photochemical and photophysical studies of linked donor/acceptor photosensitizer systems will lead to a better understanding on the molecular level of light-induced electron transfer systems. The results will aid in the design of more efficient molecular systems for converting light emergy into useful chemical energy.