文献类型：期刊文献

英文题名：Syntheses and coordination of linear and macrocyclic pentapyrroles possessing a fused moiety: Confusion modulated structural diversity

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

年份：2024

卷号：223

外文期刊名：DYES AND PIGMENTS

收录：;EI(收录号：20240415416838);WOS:【SCI-EXPANDED(收录号:WOS:001166642200001)】；

基金：This work at ECUST was financially supported by NSFC (22131005, 21971063, 22201074, 22075077) , 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：Porphyrinoids; Oligopyrrins; Diradicals; Coordination; Near infrared absorption

摘要：Porphyrinoids have attracted wide interest because of their vital roles in biological processes and fascinating structural and functional characters. In this work, a doubly N-confused pentapyrrane precursor N2C-P5 has been synthesized with terminal pyrrole ring A and middle pyrrole C incorporated in the N-confused mode. On this basis, pentapyrrin 1 and sapphyrin 2 have been synthesized by oxidizing N2C-P5 with 2,3-dichloro-5,6-dicyano1,4-benzoquinone (DDQ). Both 1 and 2 possess a [5.5.5]-tricyclic fused ring involving pyrrole B and the neighboring confused pyrrole C. Meanwhile, the formation of 2 involves ring closure between the terminal rings A and E. Notably, 2 exists as a diradical showing a half-field signal in the electron paramagnetic resonance (EPR) spectrum and a singlet ground state with a negative singlet-triplet energy gap of -0.50 kcal/mol. Excellent thermal stability has been observed for 2, which may be related to its large pi-conjugated framework involving the fused structure. On this basis, 1 and 2 were treated with Cu(acac)2 to afford Cu(II) complexes 3 and 4, respectively. As a result, an acetylacetonyl moiety is attached at the terminal pyrrole ring E to afford an NNNO coordination environment for complex 3, and the sapphyrin macrocycle of 2 has been cleaved between rings A and B to afford a fused pentapyrrin ligand, furnishing an NNNN coordination environment for complex 4, in which a pentafluorophenyl-ketal group generated during the ring cleavage reaction is attached to ring A, and it can be hydrolyzed to the corresponding pentafluorobenzoyl substituent to afford complex 5. Compared with free bases 1 and 2, complexes 3-5 show more intense low-energy near-infrared (NIR) absorption bands at ca. 791, 926 and 907 nm, respectively. This work provides an effective approach for the syntheses of linear and macrocyclic oligopyrroles with intriguing structures and properties by oxidizing oligopyrranes with precisely designed numbers and positions of N-confused pyrroles.