Synthesis and Self-Assembly of New Polycyclic Aromatic Hydrocarbons

新型多环芳烃的合成与自组装

• 批准号: RGPIN-2020-05293
• 负责人: Maly, Kenneth
• 金额: $ 2.11万
• 依托单位: Wilfrid Laurier University
• 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=747992
• 关键词: Synthesis; Self; Assembly; New; Polycyclic

Materials based on conjugated aromatic compounds show potential for the next generation of organic electronic devices, including displays and solar cells. Design of these materials requires the ability to tune molecular properties, as well as the ability to control how molecules are organized and positioned in media such as crystalline solids or liquid crystals. The proposed research uses synthetic organic chemistry to prepare new polycyclic aromatic compounds that are designed to self-assemble in predictable ways and aims to understand how molecular structure affects this self-assembly. Ultimately, this research program will provide insight to guide the design of new functional materials. Over the next five years, the research program will focus on three main areas: (i) Disk-shaped molecules composed of polycyclic aromatic hydrocarbons (PAHs) and peripheral flexible alkyl side chains can form columnar liquid crystal phases. Our studies have examined how modifications to molecular structure affect liquid crystalline properties. Based on our previous work, we will design new columnar liquid crystalline molecules based on electron-deficient PAHs and large disk-shaped molecules to probe the effect of structural modifications on liquid crystalline properties. In addition, we will prepare compounds can serve as molecular building blocks for the construction of extended, covalently linked frameworks. (ii) In contrast to the planar disk-shaped molecules described above, non-planar aromatic compounds often do not stack as effectively and engage in intermolecular interactions with other types of molecules, including fullerenes or carbon nanotubes. We will prepare new non-planar aromatic compounds and explore their ability to bind small molecules such as electron-deficient aromatic compounds and fullerenes. For example, we will prepare extended versions of tetraphenylenes with larger polycyclic aromatic units, forming compounds with a distinct cavity that is capable of binding other molecules, such as small aromatic compounds like TNT and fullerenes. (iii) We have shown that new luminescent liquid crystalline compounds can be prepared by nucleophilic aromatic substitution reactions of tetrafluoroterephthalonitrile with catechol derivatives. We have extended this methodology to incorporate other heteroatoms in these polycyclic systems and have demonstrated that heteroatom substitution has a dramatic impact on solid state organization and luminescence. Using our methodology, we will focus on the preparation of functional materials such as electron accepting materials for organic electronics. We will also use this approach to prepare more complex architectures where awkward molecular shape prevents effecting packing. These materials may serve as porous molecular solids for the encapsulation of small molecules, gas storage, or catalysis.

基于共轭芳香化合物的材料显示了下一代有机电子器件的潜力，包括显示器和太阳能电池。这些材料的设计需要能够调节分子的性质，以及控制分子在晶体固体或液晶等介质中的组织和定位的能力。这项拟议的研究使用合成有机化学来制备新的多环芳香化合物，这些化合物旨在以可预测的方式进行自组装，并旨在了解分子结构如何影响这种自组装。最终，这项研究计划将为指导新功能材料的设计提供见解。未来五年，该研究计划将集中在三个主要领域：(I)由多环芳烃(PAHs)和外围柔性烷基侧链组成的盘状分子可以形成柱状液晶相。我们的研究考察了分子结构的改变如何影响液晶性能。在前人工作的基础上，我们将设计基于缺电子多环芳烃和大分子盘状液晶的新型柱状液晶分子，以探索结构修饰对液晶性能的影响。此外，我们还将准备可用作构建延伸的共价连接框架的分子构建块的化合物。(Ii)与上述平面盘状分子相比，非平面芳香族化合物通常不会有效堆积，并与包括富勒烯或碳纳米管在内的其他类型的分子发生分子间相互作用。我们将制备新的非平面芳香族化合物，并探索它们与小分子如缺电子芳香族化合物和富勒烯的结合能力。例如，我们将制备具有更大多环芳烃单元的扩展版本的四苯基，形成具有独特空腔的化合物，该化合物能够结合其他分子，如TNT和富勒烯等小芳香族化合物。(3)通过四氟对苯二甲腈与邻苯二酚衍生物的亲核芳香取代反应，合成了新型发光液晶化合物。我们已经将这种方法扩展到这些多环体系中的其他杂原子，并证明了杂原子取代对固态组织和发光有显著的影响。利用我们的方法，我们将专注于功能材料的制备，例如用于有机电子的电子接受材料。我们还将使用这种方法来制备更复杂的结构，其中笨拙的分子形状阻止了堆积。这些材料可用作多孔分子固体，用于包裹小分子、储存气体或催化。