Transition Metal Complexes Containing Quinone and Hydroxyquinone Ligands

这个项目属于无机、生物无机和有机金属化学专业，属于过渡金属化学领域。该项目的重点是醌类配体的过渡金属配合物。儿茶酚酸盐和邻半醌配体的电子能级在能量上接近于金属能级，但在配合物的电子结构中仍然是离散的。醌配合物通常表现出强烈的低能电荷转移跃迁，与配体和金属轨道之间的电子转移相对应。研究了影响金属和醌的相对能量的影响，以确定可用于调节能量分离的参数，结果表明，决定金属和醌配体之间电荷分布的因素包括金属轨道能量，其他配体的身份和配合物的总电荷。这些研究将扩展到平面醌配合物，显示出金属之间和醌配体之间强烈的分子间相互作用。这些配合物的光电性能和导电性能将被研究，重点是它们作为盘状中间相液晶的应用。本文将在氧原子转移反应、烯烃环氧化反应和光化学水氧化反应的体系中，研究金属螯合物的氧配体在螯合物-金属CT波段辐照下的失稳。学习如何通过改变金属原子所结合的分子来调整金属原子的性质，对于控制金属原子在催化剂中的功能以及更好地理解金属原子在生物系统中的功能至关重要。

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.