文献类型：期刊文献

英文题名：Dimerization of Hexaphyrin with an Appendant Pyrrole Possessing a Reactive Site to Alleviate the Steric Hindrance

作者：Xie, Yongshu[1,2];Su, Guangxian[1,2];Ishida, Masatoshi[3];Zhu, Bin[1,2];Baryshnikov, Glib[4];Sha, Feng[1,2];Li, Chengjie[1,2];Wu, Xinyan[1,2];Agren, Hans[5];Furuta, Hiroyuki[6];Li, Qizhao[1,2]

机构：[1]East China Univ Sci & Technol, Inst Fine Chem,Sch Chem & Mol Engn, Frontiers Sci Ctr Materiobiol & Dynam Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Inst Fine Chem, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Feringa Nobel Prize Scientist, Shanghai 200237, Peoples R China;[3]Tokyo Metropolitan Univ, Grad Sch Sci, Dept Chem, Tokyo 1920397, Japan;[4]Linkoping Univ, Dept Sci & Technol, Lab Organ Elect, SE-60174 Norrkoping, Sweden;[5]Uppsala Univ, Dept Phys & Astron, SE-75120 Uppsala, Sweden;[6]Kyushu Univ, Grad Sch Engn, Dept Appl Chem, Fukuoka 8190395, Japan

年份：2025

卷号：147

期号：6

起止页码：5368

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20250617812657);WOS:【SCI-EXPANDED(收录号:WOS:001411221300001)】；

基金：This work at ECUST was financially supported by the Science and Technology Commission of Shanghai Municipality (24DX1400200), NSFC (22131005, 22201074, 22075077, and 21908055), the Program of Introducing Talents of Discipline to Universities (B16017), the Fundamental Research Funds for the Central Universities, Shanghai Rising-Star Program (23QA1402100), Shanghai Pujiang Program (24PJD024), and Natural Science Foundation of Shanghai (23ZR1415600 and 22ZR1416100). 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). The work in TMU was supported by a JST PRESTO (JPMJPR2103) and in Kyushu was endorsed by a Grants-in-Aid (JP20H00406 and JP21K18984) from the Japan Society for the Promotion of Science (JSPS). 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：Aromatization - Catalysis - Chelation - Dimerization - Infrared absorption - Pyridine - Red Shift - Regioselectivity

摘要：Oxidative dimerization of pi-conjugated molecules is a straightforward approach for effectively extending pi-conjugation and absorption features. However, it is challenging to construct dimeric species of bulky pi-conjugated frameworks because of the steric hindrances and/or poor regioselectivity. To address these issues, a pyrrole unit has been regioselectively appended to the alpha position of N-confused hexaphyrin (1.1.1.1.1.0) 1 by a facile acid-catalyzed condensation reaction, leading to the formation of pyrrole-appendant 2. Subsequent oxidation of 2 yielded an inner-fused monomer 2F and two fused dimeric species, namely, (2F) 2 a and (2F) 2 b. In contrast, oxidation of the corresponding Ni(II) complex 2Ni generated dimer (2Ni) 2 . Subsequent demetalation resulted in the formation of bipyrrole-linked freebase dimer (2) 2 , which could chelate Ni(II) and Cu(II) ions to furnish complexes (2Ni) 2 and (2Cu) 2 , respectively. In comparison to the fused dimeric species (2F) 2 a and (2F) 2 b, the nonfused dimer (2) 2 and its complexes (2Ni) 2 and (2Cu) 2 exhibit diminished local aromaticity, narrowed HOMO-LUMO gaps, and a red-shifted absorption profile that extends up to 2200 nm. These findings underscore a potent strategy for creating expanded porphyrin dimers, wherein the aromaticity and near-infrared absorption can be fine-tuned by incorporating an appendant pyrrole unit.