Principles and Practice of the Photochemistry of Coordination Compounds

配位化合物光化学原理与实践

• 批准号: 8719538
• 负责人: David McMillin
• 金额: $ 23.54万
• 依托单位: Purdue Research Foundation
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1988
• 资助国家: 美国
• 起止时间: 1988-03-01 至 1991-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8719538&HistoricalAwards=false
• 关键词: Principles; Practice; Photochemistry; Coordination; Compounds

The Inorganic, Bioinorganic, and Organometallic Program supports research in inorganic photochemistry. This research provides a fundamental basis for practical applications in the design of solar concentrators, photolithography and the treatment of certain diseases. Moreover, excited state species are being investigated in regard to various energy conversion and fuel formation schemes. This work will delineate factors influencing associative phenomena of excited-state coordination compounds. In particular the influence of donor strength on exciplex quenching and the role of donor/acceptor interactions in directing electron-transfer and energy-transfer reactions of charge-transfer (CT) states will be described in detail. Associative photosubstitution processes will also be studied. At the time same time new excited state reagents will be developed and characterized including water-soluble copper(I) complexes, copper(I) systems with high energy excited states, polynuclear systems, and photooxidizing ligand-to-metal CT states. Another objective will be to determine the influence of charge and substituent effects on copper phenanthrolines as "footprinting" reagents for DNA. Finally, the research will lead to effective photosensitizers based on conformationally constrained terpyridine ligands, and it will reveal how ligand substituents affect localization of CT states on particular ligands in mixed-ligand complexes. The methods used will include steady-state photolysis, absorption and emission spectroscopies and temperature-dependent lifetime studies. A new technique for simultaneous determination of reaction quantum yields and product spectra will also be elaborated. This research should contribute significantly to our understanding of the energies, the reactivities, and the lifetimes of excited-state transition metal complexes. It should result in the development of new DNA structure probes and potentially useful photo-induced nuclease activity.

无机，生物无机和有机物计划 支持无机光化学的研究。 本研究 为实际应用提供了基本的基础， 太阳能聚光器的设计，光刻和 治疗某些疾病。 此外，激发态物种 正在研究各种能量转换 和燃料形成方案。 这项工作将描述影响联想的因素 激发态配位化合物的现象。 在 特别是施主强度对激基复合物的影响 猝灭和供体/受体相互作用在 引导电子转移和能量转移反应， 将详细描述电荷转移（CT）状态。 还将研究缔合光取代过程。 与此同时，新的激发态试剂将被 开发并表征了包括水溶性铜（I） 络合物，具有高能量激发态的铜（I）体系， 多核系统和光氧化配体-金属CT states. 另一个目标是确定 的电荷和取代基效应对铜菲咯啉作为 DNA的“足迹”试剂。 最后，研究将 导致有效光敏剂基于构象 约束三联吡啶配体，它将揭示如何配体 取代基影响CT状态在特定 混合配体络合物中的配体。 所使用的方法将包括稳态光解， 吸收和发射光谱， 温度依赖寿命研究。 的新技术 同时测定反应量子产率和 还将阐述产品光谱。 这项研究应该 对我们理解能量有很大的贡献， 反应性和激发态跃迁的寿命 金属配合物 它应该导致新的发展， DNA结构探针和潜在有用的光诱导 核酸酶活性