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.

在化学划分的化学合成和化学结构，动力学和机制B计划的支持下，俄勒冈大学化学与生物化学系的迈克尔·海莉（Michael Haley）及其学生正在准备含有扩展的建筑的分子，以回答基本科学问题以及探索其材料。一个关键目标是开发简单的合成方法来组装这些电子感受的分子。 Haley组研究了所有新分子支架的光学，电子和/或磁性特性，重点是在光电设备（例如有机场效应晶体管（OFET）和有机光伏电动机（OPV）等光电设备中利用这些材料。该项目是基础化学和应用化学合成研究生和本科研究人员的良好培训场，并暴露于有机合成，计算化学和X射线晶体学。该计划的广播公司的影响包括当地和地区公司研究生的工业实习，与外国合作者的研究生交流，主持访问访问的延长待遇，包括来自初级本科机构（PUIS）的教授，并继续在化学研究中通过促进运动的化学研究和研究人员促进st st st st st st stement and dection（PUIS），继续研究，该组织的参与度不足。数学）。研究非苯甲苷酸分子的研究经历了复兴，因为化学家已经将其潜力作为有机半导体，其特征是其分子轨道的相对低能量以及其最高占用和最低的无能力和最低的分子轨道（分别是HOMO和LUMO）之间的较小能量差距（分别为HOMO和LUMO）。该项目通过检查（1）新的杂环融合的“推扣”衍生物，（2）非对称取代的化合物和（3）PI-Exped expected的“四边形”分子来继续进行这些系统研究。进一步的努力将扩展到全新的研究方向，例如使用（4）抗椎间盘，氧化还原活性配体和（5）有机络合物中的抗芳族N-杂环碳纤维。这些研究中开发的分子为实用应用提供了机会，尤其是在纳米技术和低成本电子学领域。从长远来看，预计这些研究将导致对电子结构与分子体系结构之间关系的更深入的理解。该奖项反映了NSF的法定任务，并通过使用基金会的知识分子优点和更广泛的影响评估标准，认为通过评估被认为是宝贵的支持。