Supramolecular Main-Group Chemistry

超分子主族化学

• 批准号: RGPIN-2016-06452
• 负责人: VargasBaca, Ignacio
• 金额: $ 2.62万
• 依托单位: McMaster University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2019
• 资助国家: 加拿大
• 起止时间: 2019-01-01 至 2020-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=686826
• 关键词: Supramolecular; Main; Group; Chemistry

Synthetic chemists have achieved exquisite control of the structure of matter at atomic scale. Their ability to selectively form and rearrange bonds between atoms is behind spectacular advances in the development of new medicinal drugs and materials for advanced technologies, to name a couple of examples. However, manipulating strong interatomic bonds often leads to unwanted side processes; chemical reactions seldom are 100% efficient. Even when by-products are obtained in small amounts and are easily removed, the limited efficiencies of such methods are greatly amplified when a synthesis must be carried out in multiple steps in order to form a large and complex structure. In many instances nature gets around such a problem by using weak bonds, which are easy to break and reconnect; this property allows thermodynamics to spontaneously “correct errors” in the structure. The adaptation of this concept to the control of molecular organization and structure is the basis of supramolecular chemistry. Most work in this area has relied on intermolecular links like hydrogen bridges and the binding of metal ions to electron-rich molecules. In recent years, the affinity of atoms of elements like iodine for atoms bearing lone pairs of electrons has received much attention and the term “halogen bond” has formally been adopted by the International Union of Pure and Applied Chemistry to describe it. Other heavy elements, also from the p-block of the periodic table, have analogous abilities to form supramolecular links.***With NSERC support, the Vargas group at McMaster University has pioneered in Canada the systematic study of the application of the supramolecular interactions formed by atoms of sulfur, selenium and tellurium (collectively called “the chalcogens”) to construct functional supramolecular structures. For example, the structure of infinite supramolecular chains of tellurium-containing molecules have been manipulated to engineer crystals with especial optical properties. Another recent achievement is the first demonstration of the ability of tellurium-oxygen “chalcogen bonds” to induce of the spontaneous assembly of discrete, well-defined, aggregates of a few molecules that together possess properties and perform the functions of new molecular entities.***Research during the new grant period will build on these successes, expanding the repertoire of supramolecular building blocks and self-assembled structures. These investigations pursue a fundamental understanding of such assemblies but knowledge derived from this is work is highly relevant to applications in areas as diverse as chemical synthesis, optical technologies, electronics and inorganic polymers. As this research program combines a wide variety of experimental and computational methods of modern chemistry, it constitutes an excellent vehicle to train highly qualified personnel for Canadian industry and academia.

举几个例子，合成化学家已经实现了对原子尺度物质结构的精确控制，他们能够选择性地形成和重新排列原子之间的键，从而在先进技术的新药物和材料的开发方面取得了巨大的进步。 ，操纵强原子间键通常会导致不需要的副反应；即使副产物数量很少并且很容易去除，这种方法的有限效率也会大大放大。为了形成一个大而复杂的结构，合成必须分多个步骤进行，在许多情况下，大自然通过使用容易断裂和重新连接的弱键来解决这个问题；这种特性允许热力学自发地“纠正错误”。这一概念对分子组织和结构的控制是超分子化学的基础，该领域的大多数工作都依赖于氢桥等分子间连接以及金属离子与富电子分子的结合。近年来，亲和力像碘这样带有孤对电子的原子的原子受到了广泛的关注，国际纯粹与应用化学联合会正式采用术语“卤键”来描述它。元素周期表中的元素，具有类似的形成超分子链接的能力。***在 NSERC 的支持下，麦克马斯特大学的 Vargas 小组在加拿大率先对硫原子形成的超分子相互作用的应用进行系统研究，硒和碲（统称为“硫属元素”）构建功能性超分子结构例如，含碲分子的无限超分子链结构已被操纵以设计具有特殊光学性质的晶体。碲-氧“硫属键”诱导离散的、明确的、几个分子聚集体自发组装的能力，这些分子一起具有新分子的特性并执行新分子的功能***新拨款期间的研究将建立在这些成功的基础上，扩大超分子构建模块和自组装结构的范围。这些研究旨在对此类组装体有基本的了解，但从这项工作中获得的知识与相关领域高度相关。由于该研究项目结合了现代化学的各种实验和计算方法，因此它成为了为加拿大工业界和学术界培养高素质人才的绝佳工具。