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

反芳香性和双自由基特征之间的相互作用：新结构和新方向

• 批准号: 2246964
• 负责人: Michael Haley
• 金额: $ 57.58万
• 依托单位: University of Oregon Eugene
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-07-01 至 2026-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2246964&HistoricalAwards=false
• 关键词: Interplay; Between; Antiaromaticity; Diradical; Character

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.

在化学系化学合成和化学结构、动力学和机理 B 项目的支持下，俄勒冈大学化学与生物化学系的 Michael Haley 教授和他的学生正在制备含有扩展结构的分子，以回答基本科学问题并探索其材料特性。一个关键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/或磁性特性，重点是这些材料在有机场效应晶体管 (OFET) 和有机光伏 (OPV) 等光电器件中的利用。该项目为基础和应用化学合成领域的研究生和本科生研究人员提供了良好的培训基地，让他们接触有机合成、计算化学和 X 射线晶体学。该计划的更广泛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交流、接待包括主要本科院校 (PUI) 教授在内的访问科学家的长期逗留，以及通过促进 STEM（科学、技术、工程和 随着化学家认识到非苯环分子作为有机半导体的潜力，其分子轨道能量相对较低，且最高占据分子轨道和最低未占据分子轨道（分别为 HOMO 和 LUMO）之间的能隙较小，对非苯环分子的研究正在复兴。 该项目旨在通过检查（1）新的杂环稠合“推拉”衍生物、（2）不对称取代的化合物和（3）π扩展的“四自由基”分子来继续这些系统研究。进一步的努力将扩展到全新的研究方向，例如它们在有机金属配合物中用作（4）抗芳香族、氧化还原活性配体和（5）抗芳香族N-杂环卡宾。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，这些研究有望使人们对电子结构和分子结构之间的关系有更深入的基本了解。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。