Aromatization-based Approaches to Designed Pi Systems with Unusual Structures and Properties

这一提议的首要目标是在芳香带(碳纳米带)的合成方面实现重大突破，芳香带不仅本身是令人着迷的分子，而且还可以作为单壁碳纳米管可控生长的种子。对这些备受欢迎的材料的追求将得到几个正在进行的和新的研究路线的支持，这些研究的结果将支持更大的目标。同时，在合成方法和策略方面的独立进展(使合成新的和日益具有挑战性的分子组件成为可能)，以及以目标为导向合成具有可开发特性的已设计的聚酰亚胺体系。*利用反向电子需求，Diels-Alder反应将直接用于双(间苯二甲酸酯)的合成，最终将被转化为具有手柄的芳香“板”，可用于创建一种环番(桥联芳香化合物)，将用于我们的芳香带方法之一。人们将寻求一种新的策略来快速构建具有潜在药用和光电性能的杂芳烃化合物。我们在多克尺度合成多官能团(强荧光多环芳烃(PAH))方面的最新进展将推动旨在开发简洁的合成路线的努力，以获得不同类型的基于芘的结构的线性和环状阵列。这些化合物有望作为传感器和发光材料的潜在应用。*我们打算以我们在环烷化学领域的长期专业知识为基础，生产各种新的环烷，特别是那些芳香成分越来越大的多环芳烃。超大尺寸的多环芳烃(纳米多环芳烃)具有理想的电学性质，它们与环芳烃的结合带来了良好的溶解性，这对它们应用到光电子器件中是很重要的。这方面的工作将涉及扩展我们现有的方法和制定新的方法和战略。一种这样的策略包括增加芳烃单元，同时缩短桥梁。这不仅将提供获得新型小应变分子(具有不寻常的化学和物理性质)的途径，而且还有可能在芳香带的合成中反复使用。其他旨在合成芳香带的项目包括合成具有适当大小、形状和官能团以构建大环体系的基于芘的环芳烃。一旦实现了这一点，将应用不同类型的化学方法将大环的组件缝合在一起，并提供直径和厚度可变的芳香带。

The top objective of this proposal is to achieve major breakthroughs in the synthesis of aromatic belts (carbon nanobelts), which are not only fascinating molecules in their own right, but may also serve as seeds for the controlled growth of single-walled carbon nanotubes. The pursuit of these highly sought-after materials will be supported by several ongoing and new lines of research, the results of which will underpin the larger goal. At the same time, stand-alone advances in synthetic methodology and strategy (to enable the synthesis of new and increasingly challenging molecular assemblies), and the target-oriented synthesis of designed pi systems with exploitable properties will be achieved. ******Work with the inverse electron demand Diels-Alder reaction will be directed towards the synthesis of bis(isophthalates), which will ultimately be converted into aromatic "boards" with handles that can be used create a type of cyclophane (bridged aromatic compound) that will be used in one of our approaches to aromatic belts. A new strategy for the rapid construction of heteroaromatic compounds with potentially useful pharmaceutical and optoelectronic properties will be pursued. Our recent advances in the multigram scale synthesis of multifunctional pyrenes (strongly fluorescent polycyclic aromatic hydrocarbons (PAH)) will drive efforts aimed at the development of concise synthetic routes to different types of linear and cyclic arrays of pyrene-based constructs. These compounds are expected to have potential applications as sensors and as luminescent materials. ******We intend to build on our longstanding expertise in the area of cyclophane chemistry to generate a variety of new cyclophanes, especially those with increasingly large PAHs as the aromatic component. Very large PAHs (nanographenes) have desirable electronic properties, and their incorporation into cyclophanes brings good solubility, which is important for their incorporation into optoelectronic devices. Work in this area will involve both the extension of our existing methodology and the development of new methods and strategies. One such strategy involves growing the aromatic unit while simultaneously shortening the bridge. This will not only provide access to new types of small strained molecules (with unusual chemical and physical properties), but also have the potential to be used iteratively in the synthesis of aromatic belts. Other projects aimed at the synthesis of aromatic belts involve the synthesis of pyrene-based cyclophanes with the appropriate size, shape and functional groups for the construction of macrocyclic systems. Once this have been achieved, different types of chemistry will be applied to sew together the components of the macrocycles and deliver aromatic belts of variable diameter and thickness.