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

化学结构、动力学和机理计划支持三一大学的Nancy S.Mills教授，他的建议描述了通过改变取代基的位置和改变环系连接的方式来评价亚丁烯类化合物的抗芳香性。吲哚体系的扩展有可能为抗芳香族物种提供更广泛的抗芳香性，因为已证明吲哚基阳离子比荧基阳离子具有更强的抗芳香性。此外，5元环的局部抗芳香性可以通过1H核磁共振位移来探讨，其固有的抗芳香性随5元环上的取代而不同。这两种方法对于其中心5元环既没有质子用作探针也没有取代可能性的荧基体系是不可能的。有机会研究取代基对吲哚系统中5-和6-成员环的影响，再加上吲哚系统具有增强的抗芳香性的潜力，这使这一系统成为一个令人兴奋的检查系统。在国家科学基金化学部化学结构、动力学和机理计划的支持下，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。三一大学有一个积极的本科生研究计划，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，并了解这些概念如何通过实验观察得到验证。此外，这项研究将帮助支持仿照德莱弗斯学者/研究员计划的博士后研究/教学助理的活动。由于三一大学拥有相对较多的研究/教学博士后研究员，目前有四名化学博士后，该系能够实施一系列活动，为这一群体在主要本科院校(PUI)成功的学术生涯做准备。

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).