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: 2022
• 资助国家: 加拿大
• 起止时间: 2022-01-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=747786
• 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，芳香带不仅本身就是令人着迷的分子，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和新的研究领域的支持，这些研究的结果将支撑更大的目标。 与此同时，合成方法和策略方面的独立进展（以实现新的且越来越具有挑战性的分子组装体的合成），以及具有可开发特性的设计 pi ​​系统的目标导向合成将得以实现。 利用逆电子需求狄尔斯-阿尔德反应将直接合成双（间苯二甲酸酯），最终将转化为带有手柄的芳香族“板”，可用于创建一种环芳烷（桥联芳香族化合物），该类型将用于我们的芳香带方法之一。 将寻求一种快速构建具有潜在有用的药物和光电特性的杂芳族化合物的新策略。 我们最近在多功能芘（强荧光多环芳烃（PAH））的多克规模合成方面取得的进展将推动旨在开发不同类型的基于芘的线性和环状阵列的简明合成路线的努力。 这些化合物预计将具有作为传感器和发光材料的潜在应用。 我们打算利用我们在环芳化学领域的长期专业知识来生产各种新型环芳，特别是那些含有越来越多的多环芳烃作为芳香族成分的环芳。 非常大的多环芳烃（纳米石墨烯）具有理想的电子特性，将它们纳入环芳烷中可带来良好的溶解度，这对于将其纳入光电器件非常重要。 该领域的工作将涉及现有方法的扩展以及新方法和策略的开发。 其中一种策略涉及生长芳香单元，同时缩短桥。 这不仅将提供新型小应变分子（具有不寻常的化学和物理性质），而且有可能在芳香带的合成中迭代使用。 其他旨在合成芳香带的项目涉及合成具有适当尺寸、形状和官能团的芘基环烷，用于构建大环系统。 一旦实现这一点，将应用不同类型的化学将大环化合物缝合在一起并提供可变直径和厚度的芳香带。