Chemistry of Strained Molecules with Radially Conjugated Pi Systems

在化学系化学合成(SYN)计划的支持下，俄勒冈大学(UO)教授拉梅什·贾斯蒂正在研究碳纳米管分子片段的合成、化学反应活性和性质。这些大环合成目标因其结构、光物理和电子性质以及超分子化学，以及它们导致碳纳米管均匀合成的潜力而引起人们的根本兴趣。这项研究计划深深植根于有机合成和新的合成方法，也涉及材料科学、生物和物理领域。PI对具有挑战性的合成目标的选择为研究生和本科生提供了合成有机策略、方法开发和反应机理方面的全面背景。此外，这些目标为学生提供了与物理学家、工程师和理论家合作的机会，以测量、利用和了解新创造的精密纳米材料的物理性质。具有径向取向的pi-体系的分子几十年来一直受到化学家的重视，但最近经历了一次复兴，因为合成方法学的新发展使以前主要是理论上的好奇变成了现在可以访问的结构。在下一个赠款期间，JASTI研究小组的目标是继续将合成边界推向越来越多的具有径向共轭圆周率系统的应变大循环。具体地说，新的圆周率延伸的带状结构、扭曲的芳烃和掺氮的纳米环都是这个赠款周期的目标。此外，还将研究乙炔嵌入纳米环的应变促进反应，作为一种使这类分子多样化的快速合成策略。为目标结构开发的方法和策略将适用于其他类型的多芳烃和新的石墨化材料(不仅仅是本提案中的特定材料)，因此具有很高的智力价值。PI还与UO暑期科学计划合作，为俄勒冈州传统上服务不足的学生群体提供突出跨学科研究和实践科学的教育经验。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Chemical Synthesis (SYN) program in the Division of Chemistry, Professor Ramesh Jasti of the University of Oregon (UO) is studying the synthesis, chemical reactivity, and properties of molecular fragments of carbon nanotubes. These macrocyclic synthetic targets are of fundamental interest for their structural, photophysical and electronic properties, and supramolecular chemistry, as well as their potential to lead to the uniform synthesis of carbon nanotubes. This research program, deeply rooted in organic synthesis and new synthetic methods, is also relevant to the fields of materials science, biology, and physics. The PI’s choice of challenging synthetic targets provides graduate and undergraduate students with a thorough background in synthetic organic strategy, methodology development, and reaction mechanism. In addition, these targets provide students opportunities to collaborate with physicists, engineers, and theorists to measure, utilize, and understand the physical properties of the newly created precision nanomaterials. Molecules with radially oriented pi-systems have been appreciated by chemists for decades, but have recently undergone a renaissance in that new developments in synthetic methodology have rendered what were previously mostly theoretical curiosities into now accessible structures. In this next grant period, the Jasti research group aims to continue to push the synthetic boundaries to the growing class of strained macrocycles with radially conjugated pi systems. Specifically, new pi-extended belt-like structures, twisted aromatics, and nitrogen doped nanohoops are all targeted in this grant cycle. In addition, strain promoted reactions of alkyne embedded nanohoops will be investigated as a rapid synthetic strategy to diversify this class of molecules. The methods and strategies developed for the targeted structures will be applicable to other types of polyaromatic hydrocarbons and new graphitic materials (not just the specific ones in this proposal) and therefore are of high intellectual merit. The PI also partners with the UO Summer Science program to provide educational experiences that highlight interdisciplinary research and hands-on science to groups of students that are traditionally underserved in the state of Oregon.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.