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

基于芳构化的方法设计具有不寻常结构和性能的 Pi 系统

• 批准号: RGPIN-2018-06813
• 负责人: Bodwell, Graham
• 金额: $ 3.5万
• 依托单位: Memorial University of Newfoundland
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2020
• 资助国家: 加拿大
• 起止时间: 2020-01-01 至 2021-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=712899
• 关键词: Aromatization; based; Approaches; Designed; Pi

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.

该提案的首要目标是在芳香带（碳纳米带）的合成方面取得重大突破，这些芳香带不仅本身是迷人的分子，而且还可以作为单壁碳纳米管受控生长的种子。 对这些备受追捧的材料的追求将得到几项正在进行的新研究的支持，其结果将支持更大的目标。 与此同时，将实现合成方法和策略的独立进展（以合成新的和日益具有挑战性的分子组装体），以及具有可开发特性的设计pi系统的靶向合成。 与反电子需求狄尔斯-阿尔德反应的工作将被导向合成双（双酸酯），其最终将被转化为具有手柄的芳香族“板”，其可用于产生一种类型的环番（桥接芳香族化合物），其将用于我们的芳香族带的方法之一。 一种新的策略，为快速建设的杂芳族化合物具有潜在的有用的药物和光电性能将追求。 我们最近在多功能芘（强荧光多环芳烃（PAH））的多克规模合成的进展将推动旨在开发简洁的合成路线，以不同类型的线性和环状阵列的芘为基础的结构的努力。 这些化合物有望在传感器和发光材料等方面具有潜在的应用前景。 我们打算利用我们在环蕃化学领域的长期专业知识，生产各种新的环蕃，特别是那些具有越来越大的多环芳烃作为芳香族组分的环蕃。 非常大的多环芳烃（纳米石墨烯）具有理想的电子性质，并且它们与环番的结合带来了良好的溶解性，这对于它们与光电器件的结合是重要的。 这一领域的工作既包括扩大我们现有的方法，也包括制定新的方法和战略。 其中一种策略是增加芳香单元，同时缩短桥。 这不仅可以获得新型的小应变分子（具有不寻常的化学和物理性质），而且有可能反复用于合成芳香带。 其他旨在合成芳香带的项目包括合成具有适当大小、形状和官能团的基于芘的环番，用于构建大环体系。 一旦实现了这一点，将应用不同类型的化学方法将大环化合物的组分缝合在一起，并提供不同直径和厚度的芳香带。