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

自组装是一种类似于通过编程将自己组装在一起的拼图的过程，是合成化学家组装大型复杂有机分子的强大工具。这个研究项目使用一种自组装方法来开发复杂的、三维的（3D）有机分子的高效途径，这种分子被称为“环烷”。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它们作为聚合物材料（塑料）前体的能力方面具有不同寻常的特性。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，发展指导经验，以及支持俄勒冈大学研究生科学小组的女性。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，可以提供平衡的离散二硫化物的热力学混合物，这些混合物可以通过硫挤压化学“动力学捕获”以产生复杂的（thia）环烷。这种有效的两步自组装和动力学捕获过程提供了可扩展的，高产的反应环烷。本研究旨在通过三个主要目的来推进这些方法，并将自组装的已知碳氢环烷前体硫环烷转化为新的环烷化合物。研究人员扩展了使用软金属离子作为指导元素合成新的2D和3D自组装离散二硫化物的方法。他们还应用硫挤压化学来“动态捕获”新的硫醚和碳氢化合物环番。最后，Johnson小组扩大了新（杂）环烷的合成规模，并研究了它们的初始性质。环烷的主客体化学、光电性能以及用作新型聚合物材料的单体进行了筛选。

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.