Tuning Antiaromaticity and Diradical Properties in Diarenoindacenes, Diindenoacenes, and Related Quinoidal Scaffolds

调节二茚并苯、二茚并苯和相关醌基支架的反芳香性和双自由基性质

• 批准号: 1954389
• 负责人: Michael Haley
• 金额: $ 49万
• 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: 2020
• 资助国家: 美国
• 起止时间: 2020-07-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1954389&HistoricalAwards=false
• 关键词: Tuning; Antiaromaticity; Diradical; Properties; Diarenoindacenes

With this award, the Chemical Synthesis Program of the NSF Chemistry Division is supporting the research of Professor Michael Haley of the University of Oregon who is synthesizing molecules known as indenoacenes and arenoindacenes. Professor Haley and his research group construct these compounds with systematic structural differences to answer fundamental questions about how these changes affect the electronic and material properties of these compounds. A key goal is to develop simple methods to construct these compounds in order to study their characteristics. Examination of the optical, electronic, and/or magnetic properties of these molecules then determines how they can be tuned and optimized for use in optoelectronic devices such as organic field effect transistors and organic photovoltaics. Professor Haley and his research group collaborate with material scientists, host visiting scientists from primarily undergraduate institutions for extended stays in their laboratory, and have continued substantial involvement of a diverse group of undergraduates in their research activities.Non-benzene-based conjugated systems, such as indenofluorenes (IFs), have been recognized for their potential as organic semiconductors characterized by low energy valence shells and a small band gap. This project aims to create extended IF structures and IF derivatives with heterocyclic groups to better understand the singlet-triplet gap in these diradical systems and to compare to the original IF system. The team also constructs novel asymmetric IF compounds to determine the effect of the loss of symmetry on fundamental properties. The molecules prepared in these studies present opportunities for practical applications in the areas of nanotechnology and low-cost electronics. This project also serves as an excellent training ground for graduate and undergraduate researchers with broad experiences in organic synthesis, computational chemistry, crystallography, and understanding the fundamental relationship between molecular structure and electronic properties.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.

有了这个奖项，NSF化学部的化学合成计划正在支持俄勒冈州大学的Michael Haley教授的研究，他正在合成被称为茚并苯和芳烃的分子。Haley教授和他的研究小组构建了这些具有系统结构差异的化合物，以回答有关这些变化如何影响这些化合物的电子和材料性质的基本问题。一个关键的目标是开发简单的方法来构建这些化合物，以研究它们的特性。然后，对这些分子的光学、电子和/或磁性性质的检查确定了如何调节和优化它们以用于光电器件，例如有机场效应晶体管和有机光致发光器件。Haley教授和他的研究小组与材料科学家合作，接待主要来自本科院校的访问科学家在他们的实验室长期停留，并继续大量参与各种本科生的研究活动。非苯基共轭体系，如茚并芴（IF），已经认识到它们作为有机半导体的潜力，其特征在于低能量价壳层和小带隙。该项目旨在创建扩展的IF结构和具有杂环基团的IF衍生物，以更好地理解这些双自由基系统中的单线态-三线态间隙，并与原始IF系统进行比较。 该团队还构建了新型的不对称IF化合物，以确定对称性丧失对基本性质的影响。这些研究中制备的分子为纳米技术和低成本电子领域的实际应用提供了机会。该项目也是培养在有机合成、计算化学、晶体学以及理解分子结构和电子性质之间的基本关系方面具有丰富经验的研究生和本科生研究人员的良好基地。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。

项目成果

Enhancing the Antiaromaticity of s -Indacene through Naphthothiophene Fusion

通过萘并噻吩融合增强 s-吲达苯的反芳香性

• DOI: 10.1021/acs.orglett.1c01514
• 发表时间: 2021
• 期刊: Organic Letters
• 影响因子: 5.2
• 作者: Warren, Gabrielle I.;Barker, Joshua E.;Zakharov, Lev N.;Haley, Michael M.
• 通讯作者: Haley, Michael M.

Comparison of Antiaromatic Properties in a Series of Structurally Isomeric Naphthothiophene‐Fused s ‐Indacenes

一系列结构异构萘并噻吩→稠合苯并苯的抗芳香性能比较

• DOI: 10.1002/chem.202301153
• 发表时间: 2023
• 期刊: Chemistry – A European Journal
• 作者: Warren, Gabrielle I.;Zocchi, Luca J.;Zakharov, Lev N.;Haley, Michael M.
• 通讯作者: Haley, Michael M.

Orbital Nature of Carboionic Monoradicals Made from Diradicals

由双自由基制成的碳离子单自由基的轨道性质

• DOI: 10.1002/chem.202300388
• 发表时间: 2023
• 期刊: Chemistry – A European Journal
• 作者: Valdivia, Abel Cardenas;Dai, Yasi;Rambaldi, Filippo;Barker, Joshua E.;Dressler, Justin J.;Zhou, Zheng;Zhu, Yikun;Wei, Zheng;Petrukhina, Marina A.;Haley, Michael M.
• 通讯作者: Haley, Michael M.

OCELOT: An infrastructure for data-driven research to discover and design crystalline organic semiconductors

• DOI: 10.1063/5.0048714
• 发表时间: 2021-05-07
• 期刊: JOURNAL OF CHEMICAL PHYSICS
• 影响因子: 4.4
• 作者: Ai, Qianxiang;Bhat, Vinayak;Risko, Chad
• 通讯作者: Risko, Chad