Retro-Bingel and Isomerization Reactions of Fullerene Derivatives via Electrochemistry: Synthesis, Mechanisms, and New Materials

迈阿密大学的Luis Echegoyen教授的这个项目专注于取代富勒烯的电化学性质，并承诺这种材料的电沉积薄层将表现出独特的可开发特性。 研究的第一个领域集中在将冠醚部分拴在富勒烯基上的化合物上。 随着阳离子移动到冠醚中，整个络合物的电化学性质发生变化。 拟议研究的第二部分是富勒烯的丙二酸酯复合物的诱导异构化，并承诺可以控制这种异构化反应，以提供一种合成途径，否则无法获得化合物。 最后，功能化富勒烯的控制电位电解用于产生捕获在分子盒框架内的游离富勒烯。 Echegoyen教授的研究小组在过去的记录基础上，为来自代表性不足群体的专业化学家提供了良好的教育记录，预计这一传统将继续下去。该项目利用了最近发现的“巴克球”化学，即衍生化它们并控制其电化学反应性的能力，以及将物种捕获在巴克球空腔内以实现相同目标的能力。 与巴基球基底连接的化学基团的多样性很广，因此反应可调性的范围相应地很大，允许设计具有特定特性的表面。 这样的技术在创造更好的电极材料和更好的化学分析传感器方面是有用的。

This project from Prof. Luis Echegoyen at the University of Miami is focused on the electrochemical properties of substituted fullerenes, with the promise that electrodeposited thin layers of such materials will exhibit unique and exploitable properties. The first area of research focuses on compounds that tether a crown ether moiety to the fullerene base. As cations move into the crown ether, the electrochemical properties of the entire complex are changed. A second part of the proposed research is the induced isomerization of malonate complexes of the fullerenes, with the promise that this isomerization reaction can be controlled to provide a synthetic route to otherwise inaccessible compounds. Finally, controlled potential electrolysis of functionalized fullerenes is used to produce free fullerenes that are trapped within a molecular box framework. Prof. Echegoyen's research group has an excellent record for the education of professional chemists from underrepresented groups, based on past record, and that tradition is expected to continue.This project takes advantage of some recently discovered chemistry of "buckyballs", namely the ability to derivatize them and control their electrochemical reactivity, and the ability to trap species inside of the buckball cavity to accomplish the same goal. The diversity of chemical groups that link to the buckyball substrate is broad, and so the range of reactive tunability is correspondingly large, allowing surfaces with specific properties to be devised. Such a skill is useful in creating better electrode materials and better sensors for chemical analysis.