文献类型：期刊文献

英文题名：Expanded N-Confused Phlorin: A Platform for a Multiply Fused Polycyclic Ring System via Oxidation within the Macrocycle

作者：Li, Chengjie[1,2];Li, Qizhao[1,2];Shao, Jiewei[1,2];Tong, Zhangfa[3];Ishida, Masatoshi[4,5];Baryshnikov, Glib[6];Agren, Hans[6];Furuta, Hiroyuki[4,5];Xie, Yongshu[1,2]

机构：[1]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Joint Int Res Lab Precis Chem, Shanghai 200237, Peoples R China;[3]Guangxi Univ, Sch Chem & Chem Engn, Guangxi Key Lab Petrochem Resource Proc & Proc In, Nanning 530004, Peoples R China;[4]Kyushu Univ, Grad Sch Engn, Dept Chem & Biochem, Fukuoka 8190395, Japan;[5]Kyushu Univ, Ctr Mol Syst, Fukuoka 8190395, Japan;[6]KTH Royal Inst Technol, Biol Sch Biotechnol, Div Theoret Chem, SE-10691 Stockholm, Sweden

年份：2020

卷号：142

期号：40

起止页码：17195

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20204409435930);WOS:【SCI-EXPANDED(收录号:WOS:000579087600033)】；

基金：The work at ECUST was financially supported by the Shanghai Municipal Science and Technology Major Project (Grant No. 2018SHZDZX03), the International Cooperation Program of the Shanghai Science and Technology Committee (17520750100), NSFC (21971063, 21772041, 21811530005, 21702062), the Fundamental Research Funds for the Central Universities (222201717003), the Open Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology (2018k013), the Program of Introducing Talents of Discipline to Universities (B160170), the Program of Shanghai Academic Research Leader (20XD1401400), the Natural Science Foundation of Shanghai (20ZR1414100), and the China Postdoctoral Science Foundation (2019TQ0092, 2020M671016). Part of the work in Kyushu was supported by Grants-in-Aid (JP19K05439, JP19H04586, and JP20H00406) from the Japan Society for the Promotion of Science (JSPS). The authors thank the Research Center of Analysis and Test of East China University of Science and Technology for help with characterization.

语种：英文

外文关键词：Aromatic compounds - Infrared devices - Sodium Borohydride - Coordination reactions - Palladium compounds - Substitution reactions

摘要：Novel interrupted pi-conjugated macrocycles derived from expanded porphyrinoids were synthesized, and their unique reactivity was investigated in this work. The specific porphyrin analogs, so-called phlorins and isoporphyrins, possess a meso-sp(3) methylene moiety, showing inner 3NH and 1NH pyrrolic cores, respectively, and extended near-infrared (NIR) absorption. Expanded N-confused pentapyrrolic phlorin analog 1 bears an interrupted cyclic pi-conjugated system that is featured by a distinct higher HOMO and a lower LUMO. Oxidation of 1 allowed structural transformations through the expanded isoporphyrin-like species 2. One of the representative products is a spiro-carbon-bridged multiply N-fused product 3 comprising a fused [5.6.5.7.6.5]-hexacyclic ring obtained by oxidation with 2,3-dichloro-5,6-dicyano-p-benzoquinone. When magic blue was used as the oxidant, an aromatic N-confused pentaphyrin 4 was obtained via migration of one of the meso-phenyl groups to the beta-position of the neighboring pyrrolic ring. By employing the flexible cavity of 1 for metal coordination, Pd(II) complexation occurred with a specific meso oxygenation to give a bimetallic complex 5. In contrast to the rich oxidation reactions, reduction of 1 with NaBH4 resulted in the regioselective nucleophilic hydrogen substitution reaction at the para position of one of the meso-C6F5 groups. These results provide a practical approach for synthesizing novel interrupted or aromatic pi-conjugated frameworks showing NIR absorptions.