文献类型：期刊文献

英文题名：Axially N-Embedded Quasi-Carbon Nanohoops with Multioxidation States

作者：Qiu, Shuhai[1,2];Zhao, Yongye[3,4];Zhang, Li[1,2];Ni, Yong[5];Wu, Yanan[6];Cong, Huan[3,4];Qu, Da-Hui[1,2];Jiang, Wei[6];Wu, Jishan[5];Tian, He[1,2];Wang, Zhaohui[1,2,6]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat, Frontiers Sci Ctr Mat & Dynam Chem, Inst Fine Chem,Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Joint Int Res Lab Precis Chem & Mol Engn, Feringa Nobel Prize Sci Joint Res Ctr,Sch Chem, Frontiers Sci Ctr Materiobiol & Dynam Chem,Inst F, Shanghai 200237, Peoples R China;[3]Univ Chinese Acad Sci, Chinese Acad Sci, Key Lab Photochem Convers & Optoelect Mat, Tech Inst Phys & Chem, Beijing 100190, Peoples R China;[4]Univ Chinese Acad Sci, Chinese Acad Sci, Beijing 100190, Peoples R China;[5]Natl Univ Singapore, Dept Chem, Singapore 117543, Singapore;[6]Tsinghua Univ, Dept Chem, Key Lab Organ Optoelect & Mol Engn, Beijing 100084, Peoples R China

年份：2023

卷号：5

期号：8

起止页码：1763

外文期刊名：CCS CHEMISTRY

收录：WOS:【ESCI(收录号:WOS:001125389100006)】；

基金：This work was financially supported by the National Natural Science Foundation of China (grant nos. 22235005, 21871084, and 21790361), the Shanghai Municipal Science and Technology Major Project (grant no. 2018SHZDZX03), the Fundamental Research Funds for the Central Universities, the Programme of Introducing Talents of Discipline to Universities (grant no. B16017), the Program of Shanghai Academic/Technology Research Leader (grant no. 19XD1421100), the Shanghai Science and Technology Committee (grant no. 17520750100), and the China Postdoctoral Science Foundation (grant no. 2020M671018).

语种：英文

外文关键词：N-embedded macrocycles; Yamamoto coupling reactions; geometrical structures; redox properties; dications

摘要：The incorporation of heteroatoms into carbon nano-hoops can significantly overcome aromatic stabilization energy and enrich their physicochemical properties depending on the positions and numbers of the doped atoms. Utilizing a V-shaped dipyreneo [c,e]dihydrophenazine as the building block, herein we report a novel kind of axially N-embedded quasi-carbon nanohoops by integrating p-extended dihydropyrazine and para-phenylene subunits. Singlecrystal X-ray diffraction analyses revealed that their geometrical structures varied from droplet-shaped geometry for DPP-M and suppressed elliptical cross-section configuration for DPP-D to triangularly prismatic configuration for DPP-T. Spectroscopic measurements confirmed rich electronic properties, especially multioxidation behaviors due to the embedding of graphitic-N atoms, which are not observed in carbonaceous nanohoops and other analogs. Further investigations, including electron spin resonance spectroscopy, theoretical calculations, and single-crystal structure analyses, on the oxidized species of both DPP-D and DPP-T demonstrated their tunable open-shell ground states for the dications. This work provides a new synthetic strategy to axially N-embedded quasi-carbon nanohoops and gives insights into the design of structure-precise segments of graphitic-N-doped single-walled carbon nanotubes. [Graphics] .