Photophysics of Mono-Disperse Metal-Organic Oligomers

无机化学、生物无机化学和金属有机化学项目的这笔赠款支持佛罗里达大学化学系的Kirk S.Schanze博士对金属-有机pi共轭聚合物的光学性质的研究。几种同系单分散、金属-有机pi共轭低聚物的光物理性质将被确定为更高相对分子质量聚合物的模型。要研究的特殊化合物是单分散的苯乙炔和苯亚乙烯型低聚物，它们含有联吡啶单元，可以结合各种过渡金属离子，特别是Re(I)和Ru(II)。在这些化合物中观察到了在整个齐聚物上离域的低位金属到配体电荷转移(MLCT)激发态。除了金属中心对光学性质的影响外，还将研究齐聚物的拓扑结构、共轭长度和带隙对MLCT激发态性质的影响。一些铂-乙炔低聚物也将被研究。光物理研究将利用吸收、光致发光、光诱导吸收、瞬时FT-IR和FT-EPR光谱以及光声热计。金属-有机聚合物显示出预期的金属和有机成分的组合性质。因此，它们有可能用于需要电致变色或光折变的电子设备，或用于特定的金属离子检测。参与这个项目的研究生和本科生将在许多合成技术和复杂仪器的使用方面获得经验。

This grant in the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research on the optical properties of metal-organic pi-conjugated polymers by Dr. Kirk S. Schanze of the Department of Chemistry, University of Florida. The photophysical properties of several homologous series of mono-disperse, metal-organic pi-conjugated oligomers will be determined as models for higher molecular weight polymeric counterparts. The specifc compounds to be studied are mono-disperse phenyleneethynylene and phenylenevinylene type oligomers that contain bipyridine units that can bind a variety of transition metal ions, particularly rhenium (I) and ruthenium (II). Low-lying metal to ligand charge transfer (MLCT) excited states delocalized over the entire oligomer are observed in these compounds. In addition to the impact of the metal center on optical properties, the effects of oligomer topology, conjugation length and bandgap on the properties of the MLCT excited states will be investigated. Some platinum-acetylide oligomers will also be studied. Photophysical investigation will utilize absorption, photoluminescence, photoinduced absorption, transient FT-IR and FT-EPR spectroscopies and photoacoustic calorimetry.Metal-organic polymers exhibit properties that are a combination of those expected for the metal and organic components. For this reason, they have potential for use in electronic devices that require electrochromism or photorefractivity or in specific detection of metal ions. Graduate and undergraduate students involved in this project will gain experience in many synthetic techniques and use of sophisticated instrumentation.