文献类型：期刊文献

英文题名：Intersected Bicyclic N-Confused Corrole Dimers with Tunable Aromaticity and Topological Chirality

作者：Huang, Yanping[1,2];Zhu, Bin[1,2];Li, Shijun[1,3];Baryshnikov, Glib[4];Wang, Hailong[5];Li, Chengjie[2];Agren, Hans[6,7];Jiang, Jianzhuang[5];Xie, Yongshu[1,2];Li, Qizhao[1,2]

机构：[1]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr,Sch Ph, Frontiers Sci Ctr Materiobiol & Dynam Chem,Minist, Inst Fine Chem,Engn Res Ctr Pharmaceut Proc Chem, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr,Sch Ph, Frontiers Sci Ctr Materiobiol & Dynam Chem,Minist, Inst Fine Chem,Engn Res Ctr Pharmaceut Proc Chem, Shanghai 200237, Peoples R China;[3]Normal Univ, Coll Mat Chem & Chem Engn, Key Lab Organosilicon Chem & Mat Technol, Minist Educ, Hangzhou 311121, Peoples R China;[4]Linkoping Univ, Inst Lab Organ Elect, Dept Sci & Technol, SE-60174 Norrkoping, Sweden;[5]Univ Sci & Technol Beijing, Sch Chem & Biol Engn, Dept Chem & Chem Engn, Beijing Key Lab Sci & Applicat Funct Mol & Crystal, Beijing 100083, Peoples R China;[6]Uppsala Univ, Dept Phys & Astron, SE-75120 Uppsala, Sweden;[7]Wroclaw Univ Sci & Technol, Fac Chem, PL-50370 Wroclaw, Poland

年份：2025

卷号：147

期号：31

起止页码：28161

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20255119714614);WOS:【SCI-EXPANDED(收录号:WOS:001535100900001)】；

基金：This work at the East China University of Science and Technology (ECUST) was financially supported by NSFC (22131005, 22201074, 22075077, and 21908055), the Science and Technology Commission of Shanghai Municipality (24DX1400200), the Program of Introducing Talents of Discipline to Universities (B16017), the Fundamental Research Funds for the Central Universities, Shanghai Rising-Star Program (23QA1402100), and Shanghai Pujiang Program (24PJD024). B.Z. thanks the support from the China Postdoctoral Science Foundation (2021 M701188) and the Science and Technology Innovation Program of Suzhou City Social Development (2022SS27). G.B. is thankful for support from the Swedish Research Council (2020-04600) and from the European Union (ERC, LUMOR, 101077649). Views and opinions expressed are, however, those of the authors only and do not necessarily reflect those of the European Union or the European Research Council Executive Agency. Neither the European Union nor the granting authority can be held responsible for them. The computations were enabled by resources provided by the National Supercomputer Centre (NSC) funded by Linkoping University. The authors thank the Research Center of Analysis and Test of ECUST for compound characterization.

语种：英文

外文关键词：Aromatic compounds - Aromatization - Atoms - Copper - Copper compounds - Cyclization - Indium compounds - Metal ions - Stereochemistry - Synthesis (chemical) - Topology

摘要：Despite the successful syntheses of unique porphyrinoids by oxidative cyclization of oligopyrranes, the development of bicyclic variants with unprecedented topologies, aromaticity, and chirality remains challenging. Herein, we report the syntheses of a class of bicyclic porphyrinoids based on the oxidative cyclization of heptapyrrane P 7 . Thus, a nonsymmetrical intersected bicyclic N-confused corrole dimer 1 was synthesized, wherein two terminal pyrrolic alpha-C atoms are linked to the beta-C atoms of the middle pyrrole ring. Subsequent reduction of dimer 1 afforded dimer 2 by the attachment of two hydrogen atoms. Interestingly, 1 and 2 exhibit 18 pi aromatic-16 pi antiaromatic and 18 pi aromatic-18 pi aromatic structures, respectively, and the aromaticity of 2 can be effectively modulated by solvent polarity with contribution of the zwitterionic resonance effect. Furthermore, both 1 and 2 can chelate copper ions to form 18 pi aromatic-nonaromatic mono-Cu(III) complex 1-Cu and nonaromatic-nonaromatic bis-Cu complex 1-Cu 2 , with the absorption band edge extended to ca. 1800 nm. In addition, the distinctive structures of these compounds enable their separation into a pair of enantiomers, with (M,M)-2 and (P,P)-2 achieving the largest dissymmetry factor |g abs| of 0.015. These results indicate that oxidative cyclization of long-chain oligopyrranes holds promise for the syntheses of novel bicyclic porphyrinoids with unprecedented topologies, tunable aromaticity, and photophysical properties as well as persistent chirality.