RUI-Antiaromatic Hydrocarbon Dications and Hydrocarbon/Heterocylic Dianions: The Relationship between Delocalization and Antiaromaticity

化学结构、动力学和机制项目支持三一大学Nancy S. Mills教授的提案，该提案描述了通过改变取代基的位置和改变环系统连接方式来评估独立基指示物的抗芳香性。由于茚基阳离子已被证明比氟基阳离子具有更强的抗芳性，因此向茚基体系的扩展有可能为抗芳物质提供更广泛的抗芳性。此外，通过1H NMR位移可以探测到5元环的局部抗芳性，其固有的抗芳性会随着5元环上的取代而变化。这两种方法对于中心5元环既没有质子作为探针也没有取代可能性的氟芴基体系是不可能的。有机会研究取代基对独立基体系中5元环和6元环的影响，再加上独立基体系的抗芳香性增强的潜力，使其成为一个令人兴奋的研究体系。并提出了将反芳香烃的研究扩展到二、三苯环七氟戊烯的研究和反芳香烃杂环的研究。在美国国家科学基金会化学部化学结构、动力学和机制项目的支持下，米尔斯博士的研究将研究芳香性，这是有机化学中的一个关键概念。这项研究将有助于解释化合物的稳定性，并指导新分子的设计。三一大学有一个活跃的本科生研究项目，强调本科生早期接触研究。学生将接触到解释芳香性关键概念的理论，并了解如何通过实验观察来验证这些概念。此外，这项研究将有助于支持研究/教学博士后助理的活动，类似于德雷福斯学者/研究员计划。由于三一大学拥有相对较大的研究/教学博士后队伍，目前化学系有四名博士后，该系能够实施一系列活动，旨在为这些人在主要的本科院校（PUIs）的学术生涯做好准备。

The Chemical Structure, Dynamics, and Mechanisms Program supports Professor Nancy S. Mills at Trinity University whose proposal describes the evaluation of the antiaromaticity of indenylidene dications through changes in the placement of substituents and changes in the manner in which the ring systems are linked together. The extension to indenyl systems has the potential to provide antiaromatic species with a broader range of antiaromaticity because the indenyl cation has been shown to be more antiaromatic than the fluorenyl cation. In addition, the local antiaromaticity of the 5-membered ring can be probed through 1H NMR shifts, and its inherent antiaromaticity varied through substitution on the 5-membered ring. These two approaches are not possible for the fluorenyl system whose central 5-membered ring possessed neither protons to be used as a probe nor the possibility of substitution. The opportunity to examine the effect of substituents on both 5-and 6-membered rings in the indenyl system, coupled with the potential for enhanced antiaromaticity of an indenyl system makes this an exciting system for examination. Extension of the investigations of antiaromatic hydrocarbon dianions to the dianion of di-and tribenzannulated heptafulvalene and to antiaromatic heterocyclic dianions is also proposed.With the support of the Chemical Structure, Dynamics, and Mechanisms Program in the Chemistry Division at the National Science Foundation, Dr. Mills' research will study aromaticity, a key concept in organic chemistry. This study will help to explain the stability of chemical compounds and guide the design of new molecules. Trinity University has an active undergraduate research program that emphasizes the early exposure of undergraduates to research. Students will be exposed to the theory that explains the key concepts of aromaticity and see how these are validated by experimental observations. In addition, the research will help support the activities of a research/teaching post-doctoral associate, patterned after the Dreyfus Scholar/Fellow program. Because Trinity University has a relatively large cohort of research /teaching post-doctoral fellows, currently four in chemistry, the department is able to implement a series of activities designed to prepare this group for successful academic careers at principally undergraduate institutions (PUIs).