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

自组装是合成化学家组装大型复杂有机分子的有力工具。这项研究计划使用自组装方法来开发高效的路线，以获得复杂的三维(3D)有机分子，即所谓的“环芳烃”。这些新的化学实体在与光的相互作用、笼状结构中的“客体”分子的结合以及作为聚合物材料(塑料)的前体的能力方面具有不同寻常的性质。这项研究的一个更广泛的影响是，可能为对二甲苯工业聚合过程开发新的积木，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将基础科学发现转化为应用。新的职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，以及支持俄勒冈大学的女性研究生科学小组。本科生研究人员参与该项目也仍然是一个优先事项。该项目专门寻求推进一项初步发现，表明用碘对硫醇配体和烟原源进行简单处理可以提供离散二硫化物的平衡热力学混合物，这些混合物可以通过硫磺挤出化学“动力学捕获”，从而产生复杂的(硫杂)环番。这种高效的自组装和动力学捕获的两步过程提供了可扩展的高产率反应中的环番。本研究旨在改进这些方法，并通过三个主要目标将已知的碳氢环烷前驱体自组装的硫代环番化合物转化为新的环番化合物。研究人员扩展了利用软金属离子作为导向元素来合成新的2D和3D自组装离散二硫化物的方法。他们还应用硫磺挤出化学“动力学捕获”新的硫醚和碳氢化合物环烷。最后，约翰逊小组放大了新的(杂环)环烷的合成并研究了它们的初始性质。对环芳烃的主客体化学、光电性能进行了筛选，并将其用作新型聚合物材料的单体。

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.