从含有八元环的稠环芳烃到具有负曲率的碳纳米结构:进展与展望  

From Polycyclic Arenes Containing Eight-Membered Rings to Negatively Curved Nanocarbons:Progress and Outlook

作　　者：缪谦 杨代月[1,3] Qian Miao;Daiyue Yang(Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China;Department of Chemistry,the Chinese University of Hong Kong,Hong Kong 999077,China;College of Chemistry and Chemical Engineering,Henan Normal University,Xinxiang 453007,China)

机构地区：[1]中国科学院上海有机化学研究所沪港合成化学联合实验室,上海200032 [2]香港中文大学化学系,香港999077 [3]河南师范大学化学化工学院,新乡453007

出　　处：《化学进展》2020年第11期1835-1845,共11页Progress in Chemistry

基　　金：裘槎基金会(裘槎优秀科研者奖)资助。

摘　　要：完全由sp^2杂化的碳原子所构成的同素异形体呈现出或平坦或弯曲的面,该表面的曲率反映了碳纳米结构的整体几何特性。完全由六元环构成的石墨烯的曲率为零;由六元环和五元环共同构成的富勒烯的曲率为正;向碳原子的六边形网格中引入七元环或八元环则产生形如马鞍的面,其曲率为负。具有负曲率的三维周期性碳结构被命名为马凯晶体或碳施瓦茨体,是碳纳米科学研究长期追寻的目标,然而至今仍未被确定无疑地合成出来。为精确合成具有负曲率的碳纳米结构,一种至下而上的策略是先合成具有负曲率的稠环芳烃,再以其为模板或单体来制备更大的碳纳米结构。具有负曲率的稠环芳烃可以通过向稠环骨架中引入七元或八元环来设计、合成,表现出一些平面稠环芳烃所不具有的结构特征与性质。本文以包含八元环的稠环芳烃为例,介绍具有负曲率的稠环芳烃的设计、合成、立体动力学及其他特征,并展望具有负曲率的碳纳米结构的新研究方向。Carbon allotropes comprised exclusively of sp^2 hybridized carbon atoms present flat or curved surface,whose overall geometric feature is reflected by its curvature.Consisting of six-membered rings exclusively,graphene has zero curvature.Five-membered rings induce positive curvature as displayed in fullerenes;while seven-or eight-membered rings in a hexagonal lattice of carbon induce negative curvature as displayed in a saddle-shaped surface.Negatively curved nanocarbons of three-dimensional periodic structures are named as Mackay crystal or carbon schwarzites,which are a long-sought target in carbon nanoscience,but have not been synthesized unambiguously yet.A bottom-up approach to negatively curved nanocarbons involves synthesis of negatively curved polycyclic arenes,which can then be used as templates or monomers in synthesis of larger nanocarbons.Negatively curved polycyclic arenes,which can be designed and synthesized by introduction of seven or eight-membered rings into polycyclic aromatic frameworks,exhibit structural characteristics and properties that are not available to planar polycyclic arenes.Taking the polycyclic arenes containing eightmembered rings as examples,this review article describes research in the design,synthesis,stereochemical dynamics,and other characteristics of negatively curved polycyclic arenes,and provides an outlook for new directions in the research of negatively curved nanocarbons.

关 键 词：稠环芳烃 碳纳米结构 负曲率 八元环 有机合成 立体化学 

分 类 号：O625.[理学—有机化学] O625.1[理学—化学]