Negatively Curved Heptagon-Containing Carbon π-Scaffolds

sp2杂化碳的框架为有机材料中使用的一些最令人兴奋的分子提供了基础。因此，极大的兴趣围绕着这些结构的属性操纵，其中包括曲率已经成为一个关键的方法。具体地说，目前的努力集中在具有挑战性的合成和研究鞍形，负弯曲的碳支架，其具有结构关系，难以捉摸的“黑碳”碳同素异形体。在这个项目中，带有七元环和负弯曲结构的结构将通过硼化介导的乙烯基萘基π-延伸方法合成。这些化合物的电子特性将得到充分表征，特别是它们的光学和固态特性将得到彻底研究。我们的目标结构将专注于负弯曲多环芳烃可实现的特殊功能，包括持久的手性，主客体化学，以及与看不见的碳同素异形体（例如Schwarzites）的结构关系。此外，将合成酰亚胺取代的变体以在n型半导体应用（即OPV和OFET器件）中利用这些独特的翘曲支架。最后，我们的灵活合成将用于构建大型和前所未有的含七边形碳带和纳米带。我们预计这些结果将大大提高负弯曲的多环芳烃的理解和它们作为功能有机材料的使用，以及自下而上的合成的黑碳石奠定基础。

Frameworks of sp2-hybridized carbon provide the basis for some of the most exciting molecules employed in organic materials. Accordingly, great interest surrounds the property manipulation of these structures, for which the inclusion of curvature has emerged as a key approach. Specifically, intense current efforts focus on the challenging synthesis and study of saddle-shaped, negatively curved carbon scaffolds which bear a structural relationship to elusive "Schwarzite" carbon allotropes. In this project, structures bearing seven-membered rings and negatively curved structures will be synthesized by a borylation-mediated vinylnaphthyl π-extension approach. The electronic properties of these compounds will be fully characterized and in particular their optical and solid-state properties will be thoroughly studied. Our target structures will focus on exceptional features attainable with negatively-curved PAHs, including persistent chirality, host-guest chemistry, and structural relationships to unseen carbon allotropes (e.g. Schwarzites). Furthermore, imide-substituted variations will be synthesized to exploit these unique warped scaffolds in n-type semiconductor applications (i.e. OPV and OFET devices). Lastly, our flexible synthesis will be used to construct large and unprecedented heptagon-containing carbon ribbons and nanobelts. We anticipate these results to greatly improve the understanding of negatively-curved PAHs and their use as functional organic materials as well as lay groundwork for the bottom-up synthesis of Schwarzites.