RUI: CAS: Quinone-Based Macrocyclic Systems for Supramolecular Applications

在化学系大分子、超分子和纳米化学项目的支持下，中央学院的杰伊·W·维克利博士计划设计和合成一类具有“捕捉和释放”能力的新的“宿主”分子。“宿主”分子有一个空腔，可以容纳一个较小的“客体”分子。这种新类别的主机的两个独特特征是：1)模块化框架，其允许控制主机的大小、形状和电子属性以选择性地结合特定客体目标，以及2)允许打开和关闭目标的绑定的可切换电子属性。将研究富电子客体分子和带负电荷的离子，如卤化物和磷酸根离子的结合性质和可逆捕获和释放。该研究旨在加深对分子间相互作用的基础认识，并为水净化和废水处理的分子受体的设计提供见解。该项目将为本科生提供研究培训机会，包括代表人数不足的群体的学生。研究成果将整合到本科实验室课程和初中和高中科学课堂的科学演示中，激发学生对科学的兴趣。这些待开发的超分子主体大环的一个值得注意的方面是，它们在受到氧化还原刺激时可以改变其电子状态，这是因为存在两个平行的面对的苯醌环。这类结构被命名为“Cambiarene”，来自拉丁语单词“cambiare”，意思是“改变”。这项研究将探索如何对嵌入的醌环进行调制，以产生不同的结构、电子和结合性质。大循环的上缘，其中包含了醌环，将从原来的形式加长和缩短，以研究如何在腔内容纳不同大小的客人，以及客人如何强烈地结合在一起，并特别注意阴离子-圆周率相互作用的贡献。宏循环的下缘将被修改，以控制腔的大小和平行对苯二酚环之间的距离。此外，还将对大环的侧基进行修饰，以增加双花烯的溶解性。这个项目应该允许开发新的小分子和大环合成方法，更好地了解阴离子与pi的相互作用，并将双芳烃确立为有用的超分子宿主分子。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Dr. Jay W. Wackerly of Central College plans to design and synthesize a new class of "host" molecules with "catch-and-release" capabilities. The "host" molecule has a cavity into which a smaller "guest" molecule can fit. Two unique features of this new class of hosts are: 1) the modular framework that enables control of the size, shape and electronic properties of the host for selective binding of a specific guest target, and 2) the switchable electronic property that permits the binding of target to be turned on and off. The binding properties and the reversible capture and release of electron-rich guest molecules and negatively charged ions, such as halide and phosphate ions, will be investigated. The research aims to gain a deeper fundamental understanding of intermolecular interactions and provide insights to the design of molecular receptor for water purification and waste treatment. The project will provide research training opportunities to undergraduate students, including students of underrepresented groups. The results of research will be integrated into undergraduate laboratory course and scientific demonstrations in the middle and high school science classrooms to arouse students’ interest in science. One notable aspect of these supramolecular host macrocycles to be developed is that they can change their electronic state when subjected to a redox stimulus due to the presence of two parallel facing quinone rings. This class of structures was given the name "cambiarene" from the Latin word "cambiare" meaning "to change". This research will explore how the embedded quinone rings can be modulated to give rise to different structural, electronic, and binding properties. The upper-rim of the macrocycle, which contains the quinone rings, will be lengthened and shortened from the original form to investigate how different sized guests can be accommodated within the cavity and how strongly guests bind with special attention being paid to the contributions from anion-pi interactions. The lower-rim of the macrocycle will be modified to control the cavity size and the distance between the parallel quinone rings. Additionally, the pendant groups of the macrocycle will be modified to increase the solubility properties of the cambiarenes. This project should allow for the development of new small molecule and macrocyclic synthetic methodology, a greater understanding of the anion-pi interaction, and the establishment of the cambiarene as a useful supramolecular host molecule.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.