Structural and Functional Diversity in Well-Defined Graphene Nanostructures

该奖项由化学学部的大分子、超分子和纳米化学项目资助。加州大学伯克利分校的T. Don Tilley教授开发了一种合成结构明确、功能多样的石墨烯纳米结构的通用方法。受欢迎的石墨烯纳米结构经过精心设计，着眼于新颖或增强的性能和未来的应用。正在开发的合成方法以碳-碳键的形成为目标，这是聚合物、材料和药物化学进步的核心。石墨烯的特殊性质引起了人们对这种材料及其子结构的广泛应用的极大兴趣，包括分子电子学、催化和传感。然而，由于缺乏可靠的合成方法来控制石墨烯的性质，这一领域的进展受到了严重阻碍。该项目为青年科学家提供了对科学技术关键问题的广泛概述，以及在化学合成、x射线晶体学、电化学、计算化学和一系列光谱技术方面的广泛技术技能。PI和参与该项目的学生组织、领导和参与外展活动，包括接待当地高中的暑期学生，并通过在附近小学的互动课程教授基本的科学原理。与自上而下的方法相比，利用有机化学构建和细化石墨烯纳米结构有望实现更高水平的性能控制。考虑到许多芳香环的融合所固有的困难，石墨烯基材料的电子特性的合成操纵，通过生成具有明确定义的尺寸、边缘结构和掺杂剂的结构，是具有挑战性的。在这个项目中，加州大学伯克利分校的T. Don Tilley教授和他的同事们正在开发一种通用的有机金属方法来解决这个环聚变的挑战，重点是炔和/或腈的[2+2+n]环加成。这种化学反应被用于几种新型的石墨烯纳米结构和相关的大型多环芳烃，所有的合成都是为了追求新的或增强的性能。利用各种吸收和发射光谱以及电化学方法，在分子水平上牢固地建立了电子和光学性质。在适当的情况下，这些特性将在超分子、单层和/或固态水平上进行探测。这项工作的一个重要方面是使用先进的物理方法来表征电子性质及其与结构的关系。

This award is funded by the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry. Professor T. Don Tilley of the University of California Berkeley is supported to develop a general approach for the synthesis of structurally well-defined and functionally diverse graphene nanostructures. The sought-after graphene nanostructures are carefully designed with an eye for novel or enhanced properties and future applications. The synthetic methods being developed target carbon-carbon bond formations, which are central to the advancement of polymer, materials, and medicinal chemistry. Graphene's extraordinary properties have generated considerable interest in this material and its substructures for many applications, including molecular electronics, catalysis, and sensing. However, progress in this area has been severely hindered by a lack of reliable synthetic methods that allow control over graphene's properties. The project provides young scientists with a broad overview of critical issues in science and technology as well as extensive technical skills in chemical synthesis, X-ray crystallography, electrochemistry, computational chemistry, and a range of spectroscopic techniques. The PI and the students involved in this project organize, lead, and participate in outreach activities, including hosting local high school summer students and teaching basic scientific principles through interactive lessons at nearby elementary schools. The construction and elaboration of graphene nanostructures using organic chemistry promises a much higher level of control over properties than that offered by top-down methods. The synthetic manipulation of electronic properties for graphene-based materials, by generation of structures with well-defined dimensionalities, edge structures, and dopants, is challenging given the inherent difficulty associated with fusion of many aromatic rings. In this project, Professor T. Don Tilley and coworkers at UC Berkeley are developing a general, organometallic approach to address this ring-fusion challenge, with a focus on [2+2+n] cycloadditions of alkynes and/or nitriles. This chemistry is being used to target several novel classes of graphene nanostructures and related large polycyclic aromatic hydrocarbons, and all syntheses are driven by the pursuit of novel or enhanced properties. Electronic and optical properties are firmly established at the molecular level using various absorption and emission spectroscopies and electrochemical methods. As appropriate, these properties are then probed at the supramolecular, monolayer, and/or solid-state levels. An important aspect to this work is the use of advanced physical methods in the characterization of electronic properties, and their relationship to structure.