Photophysical and Photochemical Investigations of New Tunable Luminescent Metal-Metal Bonded d8-d10 Exciplexes

无机，生物无机和有机化学计划的这一奖项支持奥罗诺的缅因州大学的霍华德帕特森博士研究d8-d10激基复合物，这些激基复合物表现出多种准分子发射，可以通过以下方式在紫外和可见光区域进行调谐：位置选择性激发、温度、改变溶液或固态中的浓度（碱金属卤化物主体）和/或导致可逆的写入/读取/擦除变化的受控激光照射。将进行光物理，光化学和计算研究，以评估在可调系统中建立结构-发光关系的重要因素。 先前在d10-d10复合物中观察到的宽可调性将扩展到d8-d10激基复合物，以确定可调性对以下因素的依赖性：a）不同电荷（+1，+2，+3）的阳离子; B）不同的d8-d10金属离子; c）由不同溶剂制备的复合物;和d）硫氰酸盐配体（SCN-）与氰化物（CN-）配体。光物理能量转移的研究将d8-d10供体激基复合物和镧系离子受体之间的调查。发光金属-金属键合激基复合物的光化学反应将在室温和低温下在固态和碱金属卤化物中进行研究。研究的核心是时间无关和时间分辨的发光研究、热分析、拉曼散射和红外分析、X射线和中子散射结构研究以及电子结构计算。该项目预计将提供a）具有强发光强度的可调系统的标准; B）新的发光激基复合物;以及c）对闭壳层亲金属相互作用的新见解。更好地理解这些因素将有助于可调谐固态系统的光子应用的设计。研究结果将为设计新型的固态可调谐光子系统和其他基于发光现象的器件提供有用的信息。本科生，研究生和博士后研究人员在各种仪器和技术，这将是重要的纳米科学和工程的培训也将通过拟议的研究提供。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports Dr. Howard Patterson at the University of Maine at Orono to investigate d8-d10 exciplexes exhibiting multiple excimeric emissions that can be tuned across the UV and visible regions by: site-selective excitation, temperature, varying the concentration in solution or the solid state (alkali halide hosts), and/or controlled laser irradiation that leads to reversible write/read/erase changes. Photophysical, photochemical, and computational studies will be performed in order to assess the factors that are important for establishing structure-luminescence relationships in tunable systems. The broad tunability previously observed in d10-d10 complexes will be extended to d8-d10 exciplexes in order to determine the dependence of tunability on the following factors: a) cations of different charge (+1, +2, +3); b) different d8-d10 metal ions; c) complexes prepared from different solvents; and d) the thiocyanate ligand (SCN-) vs. cyanide (CN-) ligand. Photophysical energy transfer studies will be investigated between d8-d10 donor exciplexes and lanthanide ion acceptors. The photochemical reactions of the luminescent metal-metal bonded exciplexes will be studied in the solid state and doped in alkali halides at room and cryogenic temperatures. At the heart of the investigation are time-independent and time-resolved luminescence studies, thermal analysis, Raman scattering and infrared analysis, X-ray and neutron scattering structural studies, and electronic structure calculations. The project is expected to provide a) criteria for tunable systems with strong luminescence intensities; b) new luminescent exciplexes; and c) new insights into closed-shell metallophilic interactions. A better understanding of these factors will aid in the design of tunable solidstate systems for photonic applications. The results of this research will provide useful information that can lead to the design of new solid state tunable photonic systems and other useful devices based on the luminescent phenomena. Training of undergraduates, graduate students, and post-doctoral researchers in a variety of instruments and techniques that will be important in nanoscale science and engineering will also be provided through the proposed research.