Polymers of Mixed-Valence Ruthenium Azine Complexes

罗德岛大学化学系的William B.Euler博士受到无机化学、生物无机化学和有机金属化学计划的支持，研究混价Ru-azine络合物的聚合物。该项目涉及合成和表征新的基于Ru-多氮的聚合物，以确定金属在聚合物的电子和电荷转移性能中的作用。所选择的体系将结合Ru中心作为共轭电子转移途径的一部分。聚合物的电荷转移性能将通过改变聚合物配体的寡氮桥部分的长度来改变，从而改变Ru中心之间的距离。一个理论模型预测，随着金属中心的距离变得更远，金属之间的耦合将会增加，直到齐聚氮的共轭长度达到极限。还将制备和研究双核Ru-寡氮杂-Ru化合物，作为理解聚合物这一不同寻常的预测性质的模型。所有新材料都将通过红外、核磁共振、紫外-可见-近红外光谱、循环伏安和变温电导率测量进行研究。在这个项目中，将金属化合物添加到导电聚合物中有望改变聚合物的性能，从而创造出新的非线性光学材料、催化剂和纳米结构材料。将要研究的聚合物还将有助于从根本上理解电子通过蛋白质的转移，这是生物化学中的一个重要问题。

Dr. William B. Euler of the Department of Chemistry, University of Rhode Island, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program to study polymers of mixed-valence ruthenium azine complexes. This project involves the synthesis and characterization of new ruthenium-polyazine based polymers in order to determine the role of the metal in the electronic and charge-transfer properties of the polymers. Systems selected will incorporate the ruthenium center as part of the conjugated electron-transfer pathway. The charge-transfer properties of the polymers will be modified by changing the length of the oligoazine bridge portion of the polymer ligand and thus the distance between ruthenium sites. A theoretical model predicts that as the metal sites become further apart, the coupling between metals will increase, up to the limit of the conjugation length of the oligoazine. Binuclear ruthenium-oligoazine-ruthenium compounds will also be prepared and studied as models for understanding this unusual predicted property of the polymers. All of the new materials will be studied by infrared, nuclear magnetic resonance, and ultraviolet-visible-near-infrared spectroscopies, cyclic voltammetry, and variable temperature electrical conductivity measurements. In this project the use of metal compounds appended to electrical conducting polymers is expected to modify the polymer properties, allowing for the creation of new nonlinear optical materials, catalysts, and nanostructured materials. The polymers to be studied will also help in the fundamental understanding of the transfer of electrons through proteins, an important problem in biological chemistry.