文献类型：期刊文献

英文题名：Efficient synthesis, isomerization and stepwise coordination of Heptaphyrin (1.1.1.1.1.1.0) to achieve extended NIR absorption

作者：Zhou, Yu[1,2];Huang, Yanping[1,2];Chen, Jiayi[1,2];Zhou, Mingbo[3];Zhu, Bin[1,2];Baryshnikov, Glib[4];Li, Chengjie[1,2];Agren, Hans[5,6];Song, Jianxin[3];Li, Qizhao[1,2,3];Xie, Yongshu[1,2]

机构：[1]East China Univ Sci & Technol, Engn Res Ctr Pharmaceut Proc Chem, Shanghai Key Lab Funct Mat Chem, Minist Educ,Sch Pharm,Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Engn Res Ctr Pharmaceut Proc Chem, Inst Fine Chem,State Key Lab Bioreactor Engn, Minist Educ,Sch Chem & Mol Engn,Lab Pharmaceut Cry, Shanghai 200237, Peoples R China;[3]Hunan Normal Univ, Coll Chem & Chem Engn, Key Lab Assembly & Applicat Organ Funct Mol Hunan, Minist Educ China,Key Lab Chem Biol & Tradit Chine, Changsha 410081, Peoples R China;[4]Linkoping Univ, Dept Sci & Technol, Lab Organ Elect, SE-60174 Norrkoping, Sweden;[5]Uppsala Univ, Dept Phys & Astron, Box 516, SE-75120 Uppsala, Sweden;[6]Wroclaw Univ Sci & Technol, Fac Chem, Wyb Wyspianskiego 27, PL-50370 Wroclaw, Poland

年份：2025

卷号：243

外文期刊名：DYES AND PIGMENTS

收录：;EI(收录号：20253118902392);WOS:【SCI-EXPANDED(收录号:WOS:001544302600001)】；

基金：This work at ECUST was financially supported by NSFC (22131005, 22201074, 22075077, 21908055) , 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 Pro-gram (23QA1402100) , 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 au-thority 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：Porphyrinoids; Heptaphyrin; Coordination; Near-infrared absorption

摘要：Expanded porphyrins have attracted considerable interest due to their distinctive coordination behavior and significant near-infrared (NIR) absorption. Based on the successful gram-scale synthesis of heptaphyrin (1.1.1.1.1.1.0) (1) by a multi-step method, its transformation and coordination properties have been investigated. Under heating conditions, 1 undergoes a C-N fusion reaction, transforming into a thermodynamically more stable N-fused isomer 2, with its absorption band edge extended to ca. 1750 nm. Coordination with Cu(II), Ni(II) and Pd(II) ions results in the formation of mono-metallic complexes 1Cu, 1Ni, and 1Pd, respectively. Interestingly, further chelation with Cu(II), Ni(II) and Pd(II) ions gave bis-metallic complexes 1Cu2, 1Ni2, and 1Pd2, respectively, with one of the pyrrole rings opened and converted into keto-imine moieties that participate in the coordination within the two cavities, respectively. Compared to the free base 1, the bis-metallic complexes exhibit remarkable NIR absorption, with the band edge reaching up to 1900 nm. These results demonstrate that novel heptaphyrin compounds with tunable NIR absorption properties can be synthesized via N-fusion triggered isomerization and metal coordination reactions.