Transition Metal Complexes Containing Quinone and Hydroxyquinone Ligands

该项目在无机，生物无机和有机 化学计划是在过渡金属化学领域。 该项目的重点是过渡金属配合物， 醌配体。邻苯二酚酯和邻半醌配体具有 能量接近金属能级的电子能级， 但在电子结构中保持离散， 复杂.醌络合物通常表现出强烈的低能量 电荷转移跃迁对应于 配体和金属轨道之间的电子。效应 影响金属和醌的相对能量已经被 为了确定参数， 可以用来调整能量分离，并且已经表明， 决定电荷分布的因素 包括金属轨道能量， 其他配体的身份和总电荷 复杂的。这些研究将扩展到平面醌 复合物显示出强烈的分子间相互作用， 金属和醌配体之间。照相制版和 将研究这些络合物的导电性能， 重点介绍了它们作为分散性中间相液体的应用 晶体氧代金属的氧代配体的去稳定化 通过照射的cathecholate复合物的 将在系统中研究阴极化物-金属CT带， 表现出氧原子转移反应、烯烃环氧化和 光化学水氧化 学习如何调整金属原子的性质， 它们所结合的分子对于 控制它们在催化剂中的功能， 更好地了解它们在生物系统中的功能。

This project in the Inorganic, Bioinorganic and Organometallic Chemistry Program is in the area of transition metal chemistry. The focus of the project is transition metal complexes of quinone ligands. Catecholate and o-semiquinone ligands have electronic levels which are close in energy to metal levels, but which remain discrete in the electronic structure of the complex. Quinone complexes often show intense, low-energy charge transfer transitions corresponding to transfer of electrons between ligand and metal orbitals. Effects which influence the relative energy of metal and quinone have been investigated in the interest of defining parameters which may be used to tune the energy separations, and it has been shown that the factors which determine the charge distribution between metal and quinone ligands include metal orbital energy, the identities of the other ligands and the overall charge of the complex. These studies will be extended to planar quinone complexes which show strong intermolecular interactions between metals and between quinone ligands. The photomechanical and conductive properties of these complexes will be investigated, with a focus on their application as discotic mesophase liquid crystals. Destabilization of oxo ligands of oxometal cathecholate complexes by irradiation of the cathecholate-to-metal CT band will be studied in systems which exhibit oxygen atom transfer reactions, olefin epoxidation and photochemical water oxidation. Learning how to tune the properties of metal atoms by changing the molecules to which they are bound is critical to controlling their function in catalysts and in coming to a better understanding of their function in biological systems.