Coordinatively Unsaturated Excited States

普渡大学化学系的David R.McMillin博士正在无机、生物无机和有机金属计划的支持下，研究与含有8、9或10‘d’电子的金属络合物相关的配位不饱和激发态。具体地说，这些络合物是铜的邻菲咯啉、卟啉和铂(II)的联吡啶。麦克米兰将确定参与激发态的轨道，并评估d-轨道在反应性中的作用。将使用吸收光谱、圆二色谱和发光光谱，并将测量发射寿命和偏振效应作为温度的函数。粘度法将用于DNA结合研究，以帮助确定络合物的结合模式。%这项工作的目的是表征这些络合物的发光性质，以便评估它们与各种“主体”的相互作用。这些配合物的激发态对其局域环境很敏感，因此可以作为结构探针。麦克米兰将研究它们与包括DNA和RNA在内的大分子以及与分层晶格的相互作用。研究结果对催化剂的设计有一定的指导意义。

Dr. David R. McMillin of the Chemistry Department, Purdue University, is being supported by the Inorganic, Bioinorganic, and Organometallic Program to investigate coordinately unsaturated excited states associated with metal complexes containing 8, 9, or 10 'd' electrons. Specifically, the complexes are copper phenanthrolines and porphyrins and platinum(II) terpyridines. McMillan will identify the orbitals involved in the excited states and assess the role of d-orbitals in reactivity. Absorption spectroscopy, circular dichroism, and luminescence spectroscopy will be employed and emission lifetimes and polarization effects will be measured as a function of temperature. Viscometry will be used in the DNA-binding studies to help ascertain the binding modes of the complex. %%% The objective of the work is to characterize the luminescence properties of these complexes so that their interaction with a variety of "hosts" can be assessed. The excited states of these complexes are sensitive to their local environment, so they can be used as structural probes. McMillan will investigate their interactions with macromolecules, including DNA and RNA, and with layered lattices. The results could have application to catalyst design.