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

这项无机化学、生物无机化学和金属有机化学奖支持缅因州大学奥罗诺分校的Howard Patterson博士研究d8-d10激基缔合物，这些激基缔合物显示出多个激基缔合物发射，可以通过以下方式在UV和可见光区域进行调节：位置选择性激发、温度、改变溶液或固态(碱卤化物主体)的浓度和/或可控制的激光照射导致可逆的写入/读取/擦除变化。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。以前在D10-D10络合物中观察到的宽调谐性将扩展到D8-D10激基络合物，以确定调谐性与下列因素的相关性：a)不同电荷的阳离子(+1，+2，+3)；b)不同的d8-D10金属离子；c)从不同的溶剂制备的络合物；以及d)硫氰酸盐配体(SCN-)与氰化物(CN-)配体。将研究d8-d10给体激基络合物和稀土离子受体之间的光物理能量转移。在室温和低温下，我们将研究发光金属-金属键合激发剂在固态和掺入碱金属卤化物中的光化学反应。研究的核心是与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)新的发光激基络合物；以及c)对闭合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设计用于光子应用的可调谐固态系统。这一研究结果将为基于发光现象的新型固态可调谐光子系统的设计和其他有用器件的设计提供有用的信息。通过拟议的研究，还将为本科生、研究生和博士后研究人员提供各种仪器和技术方面的培训，这些仪器和技术将在纳米科学和工程中发挥重要作用。

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.