Supramolecular Self-Assembly and Capture as a New Route to 3D Cyclophanes

超分子自组装和捕获作为 3D 环芳的新途径

• 批准号: 1609926
• 负责人: Darren Johnson
• 金额: $ 45万
• 依托单位: University of Oregon Eugene
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-09-01 至 2021-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1609926&HistoricalAwards=false
• 关键词: Supramolecular; Self; Assembly; Capture; New

Self-assembly -- a process analogous to a puzzle programmed to put itself together -- is a powerful tool for synthetic chemists to assemble large, complex organic molecules. This research program uses a self-assembly approach to develop highly efficient routes to complex, three-dimensional (3D) organic molecules known as "cyclophanes". These new chemical entities feature unusual properties in their interaction with light, the binding of "guest" molecules within their cage-like structures, and their ability to serve as precursors for polymeric materials (plastics). One broader impact of this research is the possible development of new building blocks for the parylene industrial polymerization process that provides polymer coatings for sensitive devices and electronics. Graduate student professional development activities continue to encourage the transfer of basic science discoveries to application. New professional development opportunities include implementing individual development plans, providing opportunities for internships, developing experience in mentorship, and supporting the Women in Graduate Sciences group at the University of Oregon. The involvement of undergraduate researchers in the program continues to be a priority as well. This project specifically seeks to advance a preliminary discovery showing that simple treatment of thiol ligands and a pnictogen source with iodine provides equilibrating thermodynamic mixtures of discrete disulfides that can be "kinetically trapped" via sulfur-extrusion chemistry to yield complex (thia)cyclophanes. This efficient two-step process of self-assembly and kinetic capture provides cyclophanes in scalable, high-yielding reactions. This research seeks to advance these methods and to convert the self-assembled thiacyclophanes, which are known precursors to hydrocarbon cyclophanes, into new cyclophane compounds through three primary aims. The researchers expand methods to synthesize new 2D and 3D self-assembled discrete disulfides using soft metal ions as directing elements. They also apply sulfur-extrusion chemistry to "kinetically trap" new thioether and hydrocarbon cyclophanes. Finally, the Johnson group scales-up the syntheses of new (hetero)cyclophanes and studies their initial properties. Cyclophanes are screened for their host-guest chemistry, optoelectronic properties, and use as monomers for new polymeric materials.

自组装--一个类似于拼图的过程--是合成化学家组装大型复杂有机分子的有力工具。该研究计划使用自组装方法开发高效的路线，以复杂的三维（3D）有机分子称为“cyclophanes”。这些新的化学实体在与光的相互作用，“客体”分子在其笼状结构中的结合以及作为聚合物材料（塑料）前体的能力方面具有不寻常的特性。这项研究的一个更广泛的影响是可能为聚对二甲苯工业聚合过程开发新的构建模块，为敏感设备和电子产品提供聚合物涂层。研究生专业发展活动继续鼓励基础科学发现的应用转移。新的专业发展机会包括实施个人发展计划，提供实习机会，发展导师经验，并支持俄勒冈州大学研究生科学组的妇女。本科研究人员参与该计划仍然是一个优先事项。该项目特别寻求推进一个初步发现，表明硫醇配体和氮族元素源与碘的简单处理提供了离散二硫化物的平衡热力学混合物，其可以通过硫挤出化学“动力学捕获”以产生复杂的（硫杂）环番。这种自组装和动力学捕获的有效两步法在可扩展的高产率反应中提供环番。 本研究旨在推进这些方法，并通过三个主要目标将自组装的硫杂环蕃（已知为烃环蕃的前体）转化为新的环蕃化合物。 研究人员扩展了使用软金属离子作为定向元素合成新的2D和3D自组装离散二硫化物的方法。他们还将硫挤出化学应用于“动力学捕获”新的硫醚和烃环番。最后，约翰逊小组扩大了新的（杂）环番的合成，并研究了它们的初始性质。环番是筛选他们的主-客体化学，光电性能，并作为单体用于新的聚合物材料。