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特性，并承诺电沉积这种材料的薄层将表现出独特和可开发的特性。第一个研究领域集中在将冠醚部分连接到富勒烯基的化合物上。当阳离子进入冠醚时，整个络合物的电化学性质发生改变。该研究的第二部分是诱导富勒烯丙二酸配合物的异构化，希望这种异构化反应可以被控制，从而为合成其他难以获得的化合物提供一条途径。最后，控制电位电解功能化富勒烯被用来生产游离富勒烯被困在一个分子盒框架。根据过去的记录，Echegoyen教授的研究小组在从代表性不足的群体中培养专业化学家方面有着出色的记录，预计这一传统将继续下去。这个项目利用了最近发现的一些“巴克球”的化学性质，即对它们进行衍生化和控制其电化学反应性的能力，以及将物种困在巴克球腔内的能力，以实现同样的目标。连接到巴基球底物的化学基团的多样性是广泛的，因此反应可调性的范围相应很大，允许设计具有特定性质的表面。这种技术在制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.