文献类型：期刊文献

英文题名：A Class of Heptaphyrins with NIR Absorption Modulated by Metal Coordination and Nucleophilic Substitution

作者：Huang, Yanping[1,2];Zhu, Bin[1,2];Li, Qizhao[1,2];Baryshnikov, Glib[3];Li, Chengjie[1,2];Sha, Feng[1,2];Wu, Xin-Yan[1,2];Agren, Hans[4];Xie, Yongshu[1,2]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai Key Lab Funct Mat Chem, Key Lab Adv Mat, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Inst Fine Chem, Sch Chem & Mol Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[3]Linkoping Univ, Inst Lab Organ Elect, Dept Sci & Technol, SE-60174 Norrkoping, Sweden;[4]Uppsala Univ, Dept Phys & Astron, Box 516, SE-75120 Uppsala, Sweden

年份：2024

卷号：19

期号：19

外文期刊名：CHEMISTRY-AN ASIAN JOURNAL

收录：;EI(收录号：20244017147807);WOS:【SCI-EXPANDED(收录号:WOS:001327166700022)】；

基金：This work at ECUST was financially supported by NSFC (22131005, 22201074, 22075077, 21908055), the Fundamental Research Funds for the Central Universities, Shanghai Rising-Star Program (23QA1402100), and Natural Science Foundation of Shanghai (23ZR1415600, 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). G.B. is thankful for support from the Swedish Research Council (2020-04600) and from European Union (ERC StG 101077649). The quantum-chemical calculations were performed with computational resources provided by National Academic Infrastructure for Supercomputing in Sweden (NAISS 2024/5-73) at the National Supercomputer Centre (NSC) at Linkoeping University partially funded by the Swedish Research Council through grant agreement no. 2022-06725. The authors thank the Research Center of Analysis and Test of East China University of Science and Technology for compound characterization.

语种：英文

外文关键词：Porphyrinoids; Heptaphyrin; Coordination; Nucleophilic substitution; Near-infrared absorption

摘要：The intensive interest in expanded porphyrins can be attributed to their appealing photoelectric and coordination behavior. In this work, an N-confused heptaphyrin 1 was synthesized by an acid-catalyzed [3+4] condensation reaction. The introduction of an N-confused pyrrolic unit into the heptaphyrin macrocycle led to the formation of a figure-eight-like conformation with nonsymmetrical "NNNN" and "NNNC" coordination cavities employable for bimetallic coordination. As a result, chelation of 1 with Zn(II) and Cu(II) afforded mono-Zn(II) complex 2 and bis-Cu(II) complex 3, respectively, with the metal atoms exhibiting distorted square-planar geometries. In complex 3, an oxygen atom is attached to the alpha-C atom of N-confused pyrrole D, and thus the N and C atoms of ring D participate in coordination within the two cavities. Interestingly, treatment of 1 with Cs2CO3 in MeOH resulted in regioselective substitution of all the seven para-F atoms in the meso-C6F5 groups as well as the alpha-H of ring D by eight methoxy moieties. Complex 3 displays a red-shifted absorption band edge of ca. 2200 nm, compared to that of ca. 1600 nm observed for 1. This work provides an example of incorporating an N-confused pyrrole to construct expanded porphyrins with distinctive coordination behavior and tunable NIR absorption. A N-confused heptaphyrin 1 and its mono-Zn(II) complex 2, bis-Cu(II) complex 3 have been successfully synthesized. Interestingly, an octamethoxy-substituted compound 4 was obtained by regioselective nucleophilic methoxy substitution of 1. The absorption of heptaphyrin compounds can be effectively modulated by metal coordination and nucleophilic substitution reactions, and the maximum band edge extended up to ca. 2200 nm. image