Real-World Applications of the Antiaromaticity Concept: Assemblies, Synthetic Strategies, and Functional Properties

在休斯敦大学化学系大分子、超分子和纳米化学（MSN）项目的支持下，Judy Wu和她的团队将开展计算量子化学研究，探索、测试和验证功能富碳材料的分子水平设计原则，如光响应聚合物、纳米管和有机电子产品。预期的结果包括开发实用指南，以补充当前的实验兴趣和努力，1)制备可在光照射下改变形状或化学性质的智能聚合物，2)生长具有定制尺寸和性质的碳纳米管，用于储能和电池应用，3)设计具有优越电荷传输特性的有机分子，用于晶体管和可弯曲电子器件，总的来说，通过提供新的和有用的计算洞察力来加速功能分子和材料的发现。吴博士还共同领导和协调每月一次的理论物理有机化学（TPOC）会议。由于资金、资源、地理位置或家庭条件的限制，研究生和博士后在传统的面对面会议中代表性不足，这些会议使他们能够进行高质量的科学讨论。这些会议还为世界各地的计算有机化学小组的学生和博士后提供了一个安全的地方，可以相互分享他们的研究成果，并建立有利于他们职业发展的友谊。具体来说，本研究将激发化学家重新考虑抗芳香性概念在许多化学研究领域的实际应用。目的1研究激发态双质子转移作为光响应氢键基序设计策略的潜力。目的2旨在测试一种无金属、逐步[4+2]环加成、光化学途径生长单手性纳米管的可能性。目的3建立构效关系，解释杂原子掺杂和π环融合对多环反芳烃电子性质的影响。本研究将探讨抗芳构性在设计光响应超分子体系、开发获得有用富碳材料的合成策略以及调整膨胀π共轭材料的光电性能方面的可能作用。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 (MSN) Program in the Division of Chemistry, Judy Wu and her team at the University of Houston will carry out computational quantum chemistry research to explore, test, and validate molecular level design principles for functional carbon-rich materials, such as light-responsive polymers, nanotubes, and organic electronics. The expected outcomes include the development of practical guidelines that will complement current experimental interests and efforts, 1) to prepare smart polymers that can change shape or chemical properties when irradiated by light, 2) to grow carbon nanotubes with tailored dimensions and properties for energy storage and battery applications, 3) to design organic molecules with superior charge transport properties for transistors and bendable electronic devices, and overall, to speed up the discovery of functional molecules and materials by providing new and useful computational insight. Dr. Wu also co-leads and coordinates a monthly Theoretical Physical Organic Chemistry (TPOC) meeting. These meetings make high-quality scientific discussions accessible to graduate students and postdocs that are underrepresented in traditional in-person conferences, due to limitations in funding, resource, geographic location, or family conditions. These meetings also provide a safe place for students and postdocs in computational organic chemistry groups around the world to share their research with each other and to establish friendships that are beneficial for their career development.Specifically, the proposed research will stimulate chemist to reconsider practical applications of the concept of antiaromaticity in many areas of chemical research. Aim 1 investigates the potential of excited-state double proton transfer as a design strategy for photo-responsive hydrogen bonding motifs. Aim 2 set out to test the possibility of a metal-free, stepwise [4+2] cycloaddition, photochemical pathway for growing single-chirality nanotubes. Aim 3 seeks to establish a structure-property relationship to explain the effects of heteroatom doping and π-ring fusion on the electronic properties of polycyclic antiaromatic hydrocarbons. The proposed research will examine the possible role of antiaromaticity for designing light-responsive supramolecular systems, for developing synthetic strategies to access useful carbon-rich materials, and for tuning the optoelectronic properties of expanded π-conjugated materials.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.