文献类型：期刊文献

英文题名：Stable thiophene-embedded N-confused homoporphyrins: Partial conjugation, fusion and fluoride binding

作者：Gao, Shimin[1];Li, Chengjie[1];Baryshnikov, Glib[2,3];Agren, Hans[4];Li, Qizhao[1];Xie, Yongshu[1]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Key Lab Adv Mat, Shanghai Key Lab Funct Mat Chem, 130 Meilong Rd, Shanghai, Peoples R China;[2]Bohdan Khmelnytsky Natl Univ, Dept Chem & Nanomat Sci, UA-18031 Cherkassy, Ukraine;[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：2021

卷号：194

外文期刊名：DYES AND PIGMENTS

收录：;EI(收录号：20212710597717);WOS:【SCI-EXPANDED(收录号:WOS:000685503600007)】；

基金：This work was financially supported by NSFC (21971063, 21772041, 22075077), the Fundamental Research Funds for the Central Universities (222201717003), Program of Shanghai Academic Research Leader (20XD1401400), China Postdoctoral Science Foundation (2019TQ0092, 2020M671016), and Natural Science Foundation of Shanghai (20ZR1414100). G. B. thanks for support to Swedish Research Council (grant No. 2020-04600) and to the Ministry of Education and Science of Ukraine (project no. 0121U107533). The computations were enabled by resources provided by the Swedish National Infrastructure for Computing (SNIC) at the High Performance Computing Center North (HPC2N) partially funded by the Swedish Research Council through grant agreement no. 2018-05973.

语种：英文

外文关键词：Porphyrins; Porphyrinoids; Homoporphyrins; Calixphyrins; Expanded porphyrins

摘要：In the past decades, porphyrin analogues have attracted increasing attention in light of their unique properties and potential applications in various areas. In this work, novel nonconjugated thiophene-embedded N-confused homoporphyrins 1 and 2 as well as a fully-conjugated N-fused homoporphyrin 3 have been prepared through acid-catalyzed condensation reactions followed by oxidation. Both 1 and 2 comprise two meso-sp3-carbon atoms. However, they are insensitive to the air or common oxidants. Single crystal X-ray diffraction analysis reveals that 2 adopts a highly distorted boat-like conformation, with the NH moieties of two pyrrolic units pointing outwards and an O atom attached to the alpha position of the N-confused pyrrole unit. As a result, hydrogen-bonded dimers are formed through the intermolecular hydrogen bonds between the lactam-like moieties. In contrast to the highly distorted structure of 2, N-fused homoporphyrin 3 contains a unique 5,5,5-tricyclic fused ring, and thus demonstrates a relatively coplanar conformation except one inverted pyrrole unit. Because of the different structural characters, 3 exhibits F- binding behavior distinct from that of 1 and 2.