Design and Development of Supramolecular Mixed-Metal Systems: The Investigation of Photochemical and Electro- chemical Properties

该项目涉及设计、合成和研究具有理想的光吸收和电化学性能的新型多金属络合物的活动。将合成含有多吡啶桥联配体的铂族金属(Rh，Ir，Os，Ru)的混合金属多金属配合物。由于这些体系的多组分性质，预计它们将具有非常复杂的电子光谱和电化学。电子光谱将包含很好地进入光谱的可见区域的跃迁，这主要是由于低能的金属到配体的电荷转移跃迁。此外，对于体系中包含的所有聚伯啶配体，强烈的pi-pi星形转变将在紫外区明显。预计这些体系的电化学将以金属基氧化以及桥联和非桥联配体为基础的还原为主。对于含Rh或Ir的系统，预计在相对较低的电位下也可以进行基于金属的还原。通过金属以及桥联和非桥联配体的系统变化，将有可能深入了解光化学和电化学过程的性质。%研究规划补助金使以前没有获得联邦独立研究资助的妇女能够制定具有竞争力的研究提案。该项目涉及研究含有多个金属中心的金属络合物的光化学和电化学性质。本研究中所获得的知识将有助于更好地设计和制备具有特定光吸收性能的混合金属络合物。

The project involves planning activities for the design, synthesis, and study of novel multimetallic complexes withdesirable light absorbing and electrochemical properties. Mixed-metal multimetallic complexes of the platinum group metals (Rh, Ir, Os, Ru) which incorporate polypyridyl bridging ligands will be synthesized. These systems are expected to have very complex electronic spectra and electrochemistry due to their multicomponent nature. The electronic spectra will contain transitions well into the visible region of the spectrum, due primarily to low energy metal-to-ligand charge transfer transitions. In addition, intense pi-pi star transitions will be evident in the ultraviolet region for all polypridyl ligands contained in the system. The electrochemistry of these systems is expected to be dominated by metal-based oxidations and bridging and nonbridging ligand- based reductions. For systems containing rhodium or iridium, metal-based reductions are also expected at relatively low potentials. Through the systematic variation of the metals as well as bridging and non-bridging ligands, it will be possible to gain insight into the nature of the photochemical and electrochemical processes. %%% Research Planning Grants enable women who have not had prior independent Federal research support to develop a competitive research proposal. This project involves the study of the photochemical and electrochemical properties of metal complexes containing more than one metal center. The knowledge gained in this study will enable better design and preparation of mixed-metal complexes with specific light-absorbing properties.