o-Phenylenes: Controlled Folding and Directed Oxidative Planarization

C教授迈阿密大学（俄亥俄州）化学生物化学系的Scott Hartley获得了大分子、超分子和纳米化学计划的支持，以研究邻亚苯基（邻亚苯基）。这些形成了一类简单的共轭聚合物，最近已被证明可以自发折叠成类似于α-螺旋的构象，其中芳族堆积相互作用代替氢键。在这项工作中，正在开发控制和利用这种折叠的方法，以获得具有复杂功能性三维结构的分子。此外，邻亚苯基被用作合成石墨烯片段的基底。作为这一目标的一部分而开发的合成方法应该在自下而上制备石墨烯纳米结构方面引起广泛兴趣，并且特定的目标化合物已被确定为一类具有板状结构的新型液晶。邻苯，正如本项目中所研究的那样，将有机材料化学和纳米技术的不同但重要的领域联系起来。首先，长期以来，人们一直在寻找类似于蛋白质亚基折叠的非生物分子，因为它们在催化和能量转换等领域具有潜力。由于它们的结构简单，邻苯可能是一个重要的平台，以解决通过组装较小的折叠片段来获得复杂的功能结构的挑战。其次，石墨烯可以说是未来纳米电子学应用中最重要的单一材料。结构明确的石墨烯片对于理解石墨烯的基本性质非常重要，并且有自己的应用;在这个项目中，目标是一类不寻常的液晶，在有机电子和高性能光阀中具有潜力。该项目的更广泛的影响包括在有机合成，液晶表征，计算化学和各种形式的光谱学，以及在分子设计，构象分析，自组装和电子结构的基本概念的培训学生。一些实验的目的是为经验不足的研究人员有显着的教学价值，该项目包括一个外展工作，让高中教师参与研究经验。

Professor C. Scott Hartley of the Department of Chemistry & Biochemistry at Miami University (Ohio) is supported in an award from the Macromolecular, Supramolecular, and Nanochemistry Program for research focusing on the ortho-phenylenes (o-phenylenes). These form a simple class of conjugated polymers that have recently been shown to spontaneously fold into conformations similar to alpha-helices, with aromatic stacking interactions in place of hydrogen bonding. Methods are being developed in this work to control and exploit this folding to give molecules with complex, functional three-dimensional structures. Further, the o-phenylenes are being used as substrates for the synthesis of graphene fragments. Synthetic methods developed as part of this goal should be of broad interest in the bottom-up preparation of graphene nanostructures, and the specific target compounds have been identified as a new class of liquid crystals with board-like structures.The o-phenylenes, as investigated in this project, link disparate but important areas of organic materials chemistry and nanotechnology. First, non-biological molecules that fold analogously to protein subunits have long been sought because of their potential in areas such as catalysis and energy conversion. Because of their structural simplicity, o-phenylenes may be an important platform to address the challenge of deriving complex, functional structures by assembling smaller folded pieces. Second, graphene is arguably the most important single material under development for future applications in nanoelectronics. Structurally well-defined graphene pieces are important to understanding the basic properties of graphene and have their own applications; in this project, the targets are members of an unusual class of liquid crystals with potential in organic electronics and high performance light valves. Broader impacts of this project include the training students in organic synthesis, liquid crystals characterization, computational chemistry, and various forms of spectroscopy, as well as fundamental concepts in molecular design, conformational analysis, self-assembly, and electronic structure. Some experiments have been designed to have significant pedagogical value for less-experienced researchers; the project includes an outreach effort to get high school teachers involved in the research experience.