文献类型：期刊文献

英文题名：Pd(II) and Cu(III) Complexes of Multiply Fused Pentaphyrin Isomers with Tunable Structures and NIR Absorption

作者：Li, Mengyuan[1,2];Zhu, Bin[1,2];Li, Shijun[3];Yu, Rui[1,2];Baryshnikov, Glib[4];Li, Chengjie[1,2];Sha, Feng[1,2];Wu, Xinyan[1,2];Agren, Hans[5];Xie, Yongshu[1,2,3];Li, Qizhao[1,2]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]Chinese Univ Sci & Technol, Inst Fine Chem,Engn Res Ctr Pharmaceut Proc Chem, Sch Chem & Mol Engn,Lab Pharmaceut Crystal Engn &, Shanghai Key Lab Funct Mat Chem,State Key Lab Bior, Shanghai 200237, Peoples R China;[3]Hangzhou Normal Univ, Coll Mat Chem & Chem Engn, Key Lab Organosilicon Chem & Mat Technol, Minist Educ, Hangzhou 311121, Peoples R China;[4]Linkoping Univ, Dept Sci & Technol, Lab Organ Elect, SE-60174 Norrkoping, Sweden;[5]Uppsala Univ, Dept Phys & Astron, SE-75120 Uppsala, Sweden

年份：2024

卷号：63

期号：29

起止页码：13392

外文期刊名：INORGANIC CHEMISTRY

收录：;EI(收录号：20242916716236);WOS:【SCI-EXPANDED(收录号:WOS:001274502000001)】；

基金：This work at ECUST was financially supported by NSFC (22131005, 22201074, 22075077, 21908055), the Fundamental Research Funds for the Central Universities, the Shanghai Rising-Star Program (23QA1402100), and the Natural Science Foundation of Shanghai (23ZR1415600, 22ZR1416100). B.Z. thanks the support from the China Postdoctoral Science Foundation (2021M701188), 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 (101077649). The quantum-chemical calculations were performed with computational resources provided by the National Academic Infrastructure for Supercomputing in Sweden (NAISS 2024/5-73) at the National Supercomputer Centre (NSC) at Linkoping 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：Aromatic compounds - Coordination reactions - Copper compounds - Infrared devices - Palladium compounds - Plants (botany) - Synthesis (chemical)

摘要：Fused porphyrinoids have received increasing interest in light of their extended conjugation and unique coordination behavior. On the basis of our previously reported multiply fused pentaphyrin isomers 1 and 2, a novel isomer 3 has been synthesized in this work. 3 possesses a hexacyclic fused moiety with a nearly coplanar CCNN cavity involving an inverted pyrrole, which is slightly different from the CNNN ones of 1 and 2 involving an N-confused pyrrole. 1-3 possess cavities with three depronatable protons and thus they all can generate Cu(III) complexes. However, only 3Cu is stable under ambient conditions. On the other hand, 3 remains intact upon treatment with Pd(II) ions, while 1 and 2 could undergo structural rearrangement to accommodate Pd(II), affording 1Pd and 2Pd accompanied by the formation of a lactone ring and the addition of a methoxy group, respectively. Compared with the free bases, the complexes show distinct aromaticity and more intense near-infrared (NIR) absorption up to ca. 1600, 1170, and 1500 nm, respectively. The results indicate that the subtle modification of the linking modes between the pyrrolic units in the fused pentaphyrinoids is effective in modulating the coordination behavior for synthesizing complexes with tunable aromaticity and NIR absorption.