Reinventing Benzannulations: Electro-, Photo-, and Radical Approaches for Fusing Benzene and Cyclopentadiene Rings into Polyaromatics

在这个项目中，佛罗里达州立大学的伊戈尔·阿拉布金教授将研究复杂多环芳香化合物的结构和合成方面的基本问题，该项目由化学结构、动力学和机理B以及化学系的化学合成计划共同资助。能够在亚纳米空间精确控制原子结构和能级的分子系统可以作为光电材料、储能设备、传感器、晶体管、太阳能电池、功能聚合物等的组件。本研究旨在通过将模块化组装的前体融合到新的富碳石墨烯亚结构中，开发有效的合成方法来合成复杂的多环芳烃体系。复杂环合成设计的新概念推动了这一项目。这项工作结合了计算和实验部分，以培训每个领域的专家。该项目将为本科生、研究生和博士后水平的研究人员提供一个将学习和发现相结合的机会。结果将通过出版物和推广活动传播，包括参加公开讲座、科学研讨会、在工业、本科生和研究生院的演讲，以及录制教育视频。这项建议旨在开发新的方法，通过利用螺烯的残余应变和选择性地生成高能活性中间体，如抗芳香族物种、激发态和乙烯基来快速构建功能化的多环芳烃。此外，Alabugin研究小组的目标是通过有选择地引入五边形融合来补充现有的纯六边形石墨生成网络，以此作为设计带负电荷的富碳材料的一种方式。Alabugin教授和他的同事还将努力扩大研究中的双环反应的范围，以便在一锅操作中，转化有效地将单取代苯转化为具有精确位置的官能团和杂原子的芘和芘类似物。如果成功，这一多方面的转变将开启复杂官能团耐受苯环化学最有效的例子之一。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

In this project, funded jointly by the Chemical Structure, Dynamics, & Mechanisms B and Chemical Synthesis Programs of the Division of Chemistry, Professor Igor Alabugin at Florida State University will address fundamental questions in the structure and synthesis of complex polycyclic aromatic compounds. Molecular systems that allow precise control of atomic structure and energy levels at the sub-nanospace can serve as components of opto-electronic materials, energy storage devices, sensors, transistors, solar cells, functional polymers etc. This research aims to develop efficient synthetic approaches to complex polycyclic aromatic systems via fusions of modularly assembled precursors into new carbon-rich graphene substructures. New concepts for the design of complex ring synthesis drive this project. This work combines computational and experimental components to allow training of specialists in each area. The project will provide researchers at the undergraduate, graduate and postdoctoral levels with an opportunity to integrate learning and discovery. The results will be disseminated through publications and outreach activities, including participation in public lectures, scientific symposia, giving talks at industries, undergraduate and graduate institutions, as well as recording educational videos.This proposal sets out to develop new approaches to the rapid construction of functionalized polycyclic aromatics by using the residual strain of helicenes and selectively generated high-energy reactive intermediates such as antiaromatic species, excited states and vinyl radicals. Furthermore, the Alabugin research team is aiming to complement available purely hexagonal graphenic networks with selectively introduced pentagonal fusions as a way to design negatively charged carbon-rich materials. Professor Alabugin and his co-workers will also work to expand the scope of the double-annulation reactions under study such that, in a one-pot operation, the transformation effectively converts monosubstituted benzenes into pyrenes and pyrene analogues with precisely placed functional groups and heteroatoms. If successful, this multi-faceted transformation would open up one of the most efficient examples of complex functional group-tolerant benzannulation chemistry.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.