Principles and Practice of the Photochemistry of Coordination Compounds

无机、生物无机和有机金属项目支持无机光化学的研究。该研究为太阳能聚光器的设计、光刻和某些疾病的治疗等实际应用提供了基础依据。此外，关于各种能量转换和燃料形成方案的激发态物种正在被研究。本工作将描述影响激发态配位化合物缔合现象的因素。特别是供体强度对异构体猝灭的影响以及供体/受体相互作用在指导电荷转移（CT）态的电子转移和能量转移反应中的作用将被详细描述。结合光取代过程也将被研究。与此同时，新的激发态试剂将被开发和表征，包括水溶性铜(I)配合物、具有高能量激发态的铜(I)体系、多核体系和光氧化配体-金属CT态。另一个目标将是确定电荷和取代基效应对铜菲罗啉作为DNA“足迹”试剂的影响。最后，该研究将导致基于构象约束的三吡啶配体的有效光敏剂，并将揭示配体取代基如何影响混合配体配合物中特定配体上CT态的定位。所使用的方法将包括稳态光解，吸收和发射光谱以及温度依赖寿命研究。同时测定反应量产率和产物光谱的新技术也将得到阐述。这项研究将有助于我们对激发态过渡金属配合物的能量、反应性和寿命的理解。这将导致新的DNA结构探针和潜在有用的光诱导核酸酶活性的发展。

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.