Interplay Between Antiaromaticity and Diradical Character: New Structures and New Directions

在化学系化学合成和化学结构、动力学和机制B项目的支持下，俄勒冈大学化学与生物化学系的Michael Haley教授和他的学生们正在制备包含扩展结构的分子，以回答基本的科学问题，并探索它们的材料特性。一个关键的目标是开发简单的合成方法来组装这些电子接受分子。Haley小组研究了所有新型分子支架的光学、电子和/或磁性能，重点研究了这些材料在光电器件中的应用，如有机场效应晶体管（ofet）和有机光伏（opv）。这个项目为基础和应用化学合成的研究生和本科生提供了一个很好的训练基地，可以接触到有机合成、计算化学和x射线晶体学。该项目更广泛的影响包括研究生在当地和地区公司的工业实习，研究生与外国合作者的研究生交流，接待包括主要本科院校（PUIs）教授在内的访问科学家的长期停留，以及通过促进STEM（科学，科学，科学）中代表性不足的群体成员参与的项目，本科生继续大量参与化学研究。技术、工程和数学)。随着化学家们认识到非苯类分子作为有机半导体的潜力，它们的分子轨道能量相对较低，最高已占分子轨道和最低未占分子轨道（分别为HOMO和LUMO）之间的能量差距很小，对非苯类分子的研究已经重新兴起。本项目通过检验(1)新的杂环融合“推拉”衍生物，(2)不对称取代化合物，(3)pi扩展的“四萜”分子，继续这些系统研究。进一步的努力将扩展到全新的研究方向，如(4)抗芳香，氧化还原活性配体和(5)在有机金属配合物中的抗芳香n杂环碳烯。在这些研究中开发的分子为实际应用提供了机会，特别是在纳米技术和低成本电子领域。从长远来看，这些研究有望导致对电子结构和分子结构之间关系的更深入的基本理解。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 Chemical Synthesis and Chemical Structure, Dynamics, and Mechanisms B Programs in the Division of Chemistry, Professor Michael Haley and his students in the Department of Chemistry & Biochemistry at the University of Oregon are preparing molecules containing expanded architectures to answer fundamental scientific questions as well as to explore their materials properties. A key goal is to develop simple synthetic methods for the assembly of these electron-accepting molecules. The Haley group examines the optical, electronic, and/or magnetic properties of all new molecular scaffolds with an emphasis upon utilization of these materials in optoelectronic devices such as organic field effect transistors (OFETs) and organic photovoltaics (OPVs). This project serves as an excellent training ground for graduate and undergraduate researchers in fundamental and applied chemical synthesis, with exposure to organic synthesis, computational chemistry and x-ray crystallography. The broader impacts of this program include industrial internships of graduate students at local and regional companies, the exchange of graduate students with those of foreign collaborators, the hosting of extended stays of visiting scientists including professors from primarily undergraduate institutions (PUIs), and continued substantial involvement of undergraduates in chemical research via programs that promote participation of members of groups underrepresented in STEM (science, technology, engineering and mathematics).Research on non-benzenoid molecules has experienced a resurgence as chemists have recognized their potential as organic semiconductors characterized by the relatively low energy of their molecular orbitals and the small energy gap between their highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO, respectively). This project sets out to continue these systematic studies by examining (1) new heterocycle-fused ‘push-pull’ derivatives, (2) asymmetrically substituted compounds, and (3) pi-expanded ‘tetraradicaloid’ molecules. Further efforts will expand into completely new research directions such as their use as (4) antiaromatic, redox-active ligands and (5) antiaromatic N-heterocyclic carbenes in organometallic complexes. The molecules developed in these studies present opportunities for practical applications, particularly in the area of nanotechnology and low-cost electronics. In the longer term, these studies are expected to lead to a deeper fundamental understanding of the relationship between electronic structure and molecular architecture.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.