Syntheses and Structures of Functionalized [n]Cycloparaphenylenes and Related Carbon Nanohoops

通过这一奖项，化学合成项目支持了西弗吉尼亚大学王功权教授的基础研究。王教授将利用有机反应来构建一组名为环芳烃(CPPs)的有机分子和相关的碳纳米环。CPP的结构代表了扶手椅碳纳米管的重复环状结构中最短的部分。目前对CPPS的浓厚兴趣部分归因于将这些环状分子用作生长扶手椅式单壁碳纳米管的模板的可能性。这种合成方法比现有的经验方法具有潜在的优势，因为它可以制备直径和结构均匀的碳纳米管，这两个因素对于在各种纳米技术领域的应用至关重要，包括电子、能源和纳米光子器件。王教授将通过培训研究生设计新的合成策略，并为他们提供获得高水平实验室技能的机会，将这个项目的研究和教育部分整合在一起。在参与这一研究项目的过程中培养训练有素的合成有机化学家，将增加化学和制药行业的人力资源。此外，被选中参加西弗吉尼亚大学NSF-本科生研究体验计划和西弗吉尼亚大学暑期本科生研究体验计划的本科生将被邀请参与这一研究项目。这些本科生中的许多人来自高等教育代表性不足的人群，或者是第一代大学生。在大学期间为这些学生提供参与研究环境的机会，将鼓励他们在STEM追求职业生涯。在这项研究中，将开发合成CPPS的新方法。具体地说，利用1，4-双(卤代芳基)-1，3-二烯和双烯烃之间的Diels-Alder反应，有望制备具有不同结构特征的官能化CPP和相关的碳纳米环的前体。Diels-Alder反应的高立体选择性将两个卤代芳基取代基放置在所得到的环己烯基结构的同一侧，这对于随后的同位或交叉偶联步骤成功地形成大环CPP前体是必不可少的。用2，3-二氯-5，6-二氰基-1，4-苯二酚或其他氧化剂将CPP前驱体氧化芳构化，可得到相应的CPP。

With this award, the Chemical Synthesis program is supporting fundamental research of Professor Kung K. Wang at West Virginia University. Professor Wang will use organic reactions for the construction of a group of organic molecules called cycloparaphenylenes (CPPs) and related carbon nanohoops. The structures of CPPs represent the shortest segments of the repeating hoop-like structures of armchair carbon nanotubes. The intense current interest in CPPs is due in part to the possibility of using these hoop-like molecules as templates for growing armchair single-walled carbon nanotubes. This synthetic approach offers a potential advantage over existing empirical methods in its potential to produce carbon nanotubes of a uniform diameter and structural arrangement, two factors of critical importance for applications in a variety of nanotechnology fields, including electronics, energy, and nanophotonic devices. Professor Wang will integrate the research and educational components of this project by training graduate students in the design of new synthetic strategies and by providing them with the opportunities to acquire high-level laboratory skills. The development of well-trained synthetic organic chemists during the course of their involvements in this research project will add to the human resources for chemical and pharmaceutical industries. In addition, undergraduate students who are selected to participate in the West Virginia University NSF-Research Experiences for Undergraduates program and in the WVU Summer Undergraduate Research Experience program will be invited to participate in this research project. Many of these undergraduate students are from populations that are underrepresented in higher education or are first generation college students. Providing the opportunity to involve these students in a research environment during their college years will encourage them pursue careers in STEM. In this research, new methods will be developed for the synthesis of CPPs. Specifically, the use of the Diels-Alder reactions between 1,4-bis(haloaryl)-1,3-dienes and dienophiles are expected to produce precursors of functionalized CPPs and related carbon nanohoops with diverse structural features. The high stereoselectivity of the Diels-Alder reaction will place the two haloaryl substituents on the same side of the resulting cyclohexenyl structure, which is essential for the success of the subsequent homo- or cross-coupling step to form macrocyclic CPP precursors. Oxidative aromatization of the CPP precursors, either with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone or other oxidizing agents, is expected to lead to the corresponding CPPs.