文献类型：期刊文献

英文题名：Mono- and bis-Pd(II) complexes of N-confused dithiahexaphyrin(1.1.1.1.1.0) with the absorption and aromaticity modulated by Pd(II) coordination, macrocycle contraction and ancillary ligands

作者：Sun, Meng[1];Xie, Yongshu[1,2];Baryshnikov, Glib[3];Li, Chengjie[1];Sha, Feng[1];Wu, Xinyan[1];Agren, Hans[4];Li, Shijun[2];Li, Qizhao[1]

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

年份：2024

卷号：15

期号：6

起止页码：2047

外文期刊名：CHEMICAL SCIENCE

收录：;EI(收录号：20240215360505);WOS:【SCI-EXPANDED(收录号:WOS:001142849200001)】；

基金：This work at ECUST was financially supported by NSFC (22131005, 21971063, 22201074, 22075077), the Fundamental Research Funds for the Central Universities, Shanghai Rising-Star Program (23QA1402100), and Natural Science Foundation of Shanghai (23ZR1415600, 22ZR1416100). G. B. thanks for the Swedish National Infrastructure for Computing (SNIC) resources at the High-Performance Computing Center North (HPC2N) and the financial support of the Swedish Research Council (2018-05973, 2020-04600). 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：Aromatization - Atoms - Chlorine compounds - Ligands - Synthesis (chemical)

摘要：To further enrich the coordination chemistry of hexaphyrins and probe the underlying property-structural correlations, N-confused dithiahexaphyrin(1.1.1.1.1.0) (1) with 26 pi-electron H & uuml;ckel aromaticity was synthesized. Based on its unprecedented two unsymmetrical cavities, five palladium complexes 2, 3, 4-Ph, 4-Cl and 5 have been successfully synthesized under various coordinations. Thus, two mono-Pd(II) complexes 2 and 3 with the Pd(II) atom coordinated in the two different cavities were obtained by treating 1 with palladium reagents PdCl2, and (PPh3)(2)PdCl2 respectively. On this basis, bis-Pd(II) complexes 4-Ph and 4-Cl were synthesized by treating 2 and 3 with (PPh3)(2)PdCl2 and PdCl2, respectively. As a result, both 4-Ph and 4-Cl contain two Pd(II) atoms coordinated within the two cavities, with one of the Pd(II) atoms further coordinated to a triphenylphosphine ligand in addition to an anionic ancillary ligand of Ph- and Cl-, respectively. Notably, a further contracted mono-Pd(II) complex 5 was synthesized by treating 1 with Pd(PPh3)(4) by eliminating one of the meso-carbon atoms together with the corresponding C6F5 moiety. These complexes present tunable 26 pi aromaticity and NIR absorption up to 1060 nm. This work provides an effective approach for developing distinctive porphyrinoid Pd(II) complexes from a single porphyrinoid, without resorting to tedious syntheses of a series of porphyrinoid ligands.