RUI: Promoting Through-Space Charge Transfer via Arylene Ethynylene Templates

在化学系大分子、超分子和纳米化学项目的支持下，威斯康星大学史蒂文斯点分校的Nathan Bowling教授将设计和合成新的分子，这些分子的行为可能对现代催化剂、有机发光二极管（oled）和分子传感装置有用。具体来说，鲍林教授和他的学生将生成分子模板，使不同的分子组分接近，并研究组分的相对取向如何影响它们的相互作用和电子性质。所获得的基础知识将有助于推动下一代基于电荷转移的器件和催化剂的发展。这些化合物的合成、纯化和表征将完全由威斯康星大学史蒂文斯点分校的本科生和鲍林教授完成。具有尖端研究项目的实践经验将使这些学生在化学工业或研究生学习中脱颖而出。本项目旨在开发各种模板，以促进溶液和固态中富电子和贫电子芳香亚基之间的有效电荷转移。促进这些亚基通过空间相互作用的主要方法是一个扭曲的芳炔-乙烯基框架，亚基以分子内方式相互作用。围绕中心环的旋转迫使转子上富电子/贫电子的互补臂发生碰撞。电子（UV-vis）和晶体学（x射线）研究将深入了解亚基在这些穿越空间碰撞中的取向如何影响电荷转移行为。此外，卤素键合和金属络合将被用作驱动力来模拟扭曲芳炔-乙烯体系的几何形状。随着电荷转移预期可见颜色的开始可能为这些动态系统中主客体相互作用的比色定量提供了机会。在初始表征之后，模板设计将侧重于控制富电子/贫电子对的相对方向，用于光电、传感和催化剂应用。设计的系统有望提供一种研究电荷转移行为的方法，否则很难研究。从长远来看，这项工作有可能为下一代电子设备和光驱动催化的进步奠定基础。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, Professor Nathan Bowling of the University of Wisconsin-Stevens Point will design and synthesize new molecules that display behavior potentially useful for modern catalysts, organic light-emitting diodes (OLEDs), and molecular sensing devices. Specifically, Professor Bowling and his students will generate molecular templates that hold different molecular components in proximity and study how the relative orientation of the components affects their interactions and electronic properties. The fundamental knowledge to be gained will help advance the development of next generation, charge transfer-based devices and catalysts. Synthesis, purification, and characterization of these compounds will be performed exclusively by undergraduate students and Professor Bowling at the University of Wisconsin-Stevens Point. Hands-on experience with cutting edge research projects will position these students well to excel in the chemical industry or in graduate studies. This project aims to develop a variety of templates to promote efficient charge-transfer between electron-rich and electron-poor aromatic subunits in solution and the solid state. The primary method for promoting through-space interaction of these subunits is a twisted arylene ethynylene framework upon which the subunits interact in an intramolecular fashion. Rotation around a central tolane forces complementary electron-rich/electron-poor arms of the rotor to collide. Electronic (UV-vis) and crystallographic (x-ray) studies will provide insight into how the orientation of subunits in these through-space collisions impacts charge transfer behavior. Additionally, halogen bonding and metal complexation will be used as driving forces to mimic the geometry of the twisted arylene ethynylene systems. The onset of visible color expected with charge transfer may provide opportunities for colorimetric quantification of host-guest interaction in these dynamic systems. After initial characterization, template design will focus on controlling the relative orientations of electron-rich/electron-poor pairs for optoelectronic, sensing, and catalyst applications. The designed systems are expected to provide a method for studying charge transfer behavior that is otherwise difficult to study. In the longer term, the work has the potential to establish a foundation for advances in next-generation electronic devices and light-driven catalysis.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.