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: 2018
• 资助国家: 加拿大
• 起止时间: 2018-01-01 至 2019-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=645693
• 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.

这项提议的首要目标是在芳香带（碳纳米带）的合成上取得重大突破，这不仅是一种令人着迷的分子，而且可能为单壁碳纳米管的受控生长提供种子。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，这些研究的结果将支撑更大的目标。与此同时，合成方法和策略的独立进步（能够合成新的和越来越具有挑战性的分子组合），以及具有可开发性质的设计pi系统的靶向合成将实现。******与反电子需求Diels-Alder反应的工作将直接指向他（间苯二甲酸酯）的合成，其最终将转化为芳香“板”，其手柄可用于创建一种环烷（桥接芳香化合物），将用于我们的芳香带方法之一。一种快速构建具有潜在药用和光电子特性的杂芳烃化合物的新策略将被寻求。我们在多图尺度合成多功能芘（强荧光多环芳烃（PAH））方面的最新进展将推动旨在开发不同类型的线性和环状芘结构的简明合成路线的努力。这些化合物有望在传感器和发光材料方面有潜在的应用。******我们打算建立我们在环烷化学领域的长期专业知识，以产生各种新的环烷，特别是那些越来越大的多环芳烃作为芳香成分。非常大的多环芳烃（纳米石墨烯）具有理想的电子性能，其掺入环烷带来了良好的溶解性，这对其掺入光电器件至关重要。这方面的工作将涉及我们现有方法的扩展和新方法和战略的发展。一种这样的策略包括在种植芳香单位的同时缩短桥。这不仅将为新型的小张力分子（具有不同寻常的化学和物理性质）提供途径，而且还具有在芳香带合成中迭代使用的潜力。其他旨在合成芳香带的项目包括合成具有适当尺寸、形状和官能团的芘基环烷，用于构建大环体系。一旦实现了这一点，不同类型的化学将被应用于将大环的组成部分缝合在一起，并提供可变直径和厚度的芳香带。