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

在化学系大分子、超分子和纳米化学计划的支持下，威斯康星大学史蒂文斯分校的Nathan Bowling教授将设计和合成具有潜在应用于现代催化剂、有机发光二极管(OLED)和分子传感设备的行为的新分子。具体地说，鲍林教授和他的学生将生成将不同分子成分保持在附近的分子模板，并研究这些成分的相对取向如何影响它们的相互作用和电子性质。将获得的基础知识将有助于推动基于电荷转移的下一代设备和催化剂的发展。这些化合物的合成、提纯和表征将由本科生和威斯康星大学史蒂文斯分校的鲍林教授独家完成。在尖端研究项目方面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。该项目旨在开发各种模板，以促进溶液和固体中富电子和贫电子芳香族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亚基以分子内方式在其上相互作用的扭曲的芳香乙叉骨架。围绕中心托兰的旋转迫使转子的互补的富电子/贫电子臂发生碰撞。电子学(UV-Vis)和结晶学(x射线)研究将深入了解这些穿越空间碰撞中亚单位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，以模拟扭曲的芳撑乙炔体系的几何形状。随着电荷转移而出现的可见颜色的开始，可能为这些动态系统中的主-客体相互作用的比色量化提供机会。在初步表征之后，模板设计将重点控制用于光电子学、传感和催化剂应用的富电子/贫电子对的相对取向。所设计的系统有望为研究本来难以研究的电荷转移行为提供一种方法。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剂的进步奠定基础。这一奖项反映了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, 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.