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Jay W. Wackerly博士计划设计并合成一类具有“捕获和释放”能力的新型“宿主”分子。“宿主”分子有一个空腔，可以容纳更小的“客”分子。这种新型寄主的两个独特特点是：1)模块化框架，可以控制寄主的大小、形状和电子属性，以选择性地绑定特定的客体目标；2)可切换的电子属性，允许目标的绑定打开和关闭。富电子客体分子和负电荷离子（如卤化物和磷酸盐离子）的结合特性和可逆捕获和释放将被研究。本研究旨在加深对分子间相互作用的基本认识，并为水净化和废物处理的分子受体设计提供见解。该项目将为本科生提供研究培训机会，包括代表性不足群体的学生。将研究成果整合到本科实验课程和初高中科学课堂的科学演示中，激发学生对科学的兴趣。这些有待开发的超分子宿主大环的一个值得注意的方面是，由于存在两个平行的面向醌环，它们可以在受到氧化还原刺激时改变其电子状态。这类结构被命名为“cambiarene”，来源于拉丁语“cambiare”，意思是“变化”。本研究将探讨如何调制嵌入的醌环以产生不同的结构，电子和结合特性。包含醌环的大环的上环将从原来的形式被延长或缩短，以研究不同大小的来宾如何在腔内容纳，以及来宾结合的强度如何，特别注意阴离子π相互作用的贡献。将修改大环的下缘，以控制腔的大小和平行醌环之间的距离。此外，大环的悬垂基团将被修饰，以增加形联芳烃的溶解度。该项目将允许开发新的小分子和大环合成方法，更深入地了解阴离子- π相互作用，并建立形联芳烃作为有用的超分子宿主分子。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值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.