文献类型：期刊文献

英文题名：Porphyrindiene-Based Tandem Diels-Alder Reaction for Preparing Low-Symmetry π-Extended Porphyrins with Push-Pull Skeletons

作者：Cao, Guanyue[1];Baryshnikov, Glib[2];Chen, Chen[1];Chen, Liyuan[1];Zhao, Tengjiao[1];Fu, Shuyi[1];Jiang, Zhenhui[1];Liu, Xiujun[1];Li, Qizhao[1];Xie, Yongshu[1];Li, Chengjie[1]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat, Shanghai Key Lab Funct Mat Chem, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[2]Linkoping Univ, Dept Sci & Technol, Lab Organ Elect, SE-60174 Norrkoping, Sweden

年份：2022

卷号：87

期号：14

起止页码：9001

外文期刊名：JOURNAL OF ORGANIC CHEMISTRY

收录：;EI(收录号：20223012399897);WOS:【SCI-EXPANDED(收录号:WOS:000818717100001)】；

基金：The authors are grateful to the National Natural Science Foundation of China (NSFC 22075077, 22131005, 22108078, 21971063), the Natural Science Foundation of Shanghai (20ZR1414100, 22ZR1416100), the Program of Shanghai Academic Research Leader (20XD1401400), and the Fundamental Research Funds for the Central Universities for the financial support.

语种：英文

外文关键词：Chemical reactions - Chromophores - Ketones - Musculoskeletal system

摘要：Tandem Diels-Alder reactions of masked porphyrindienes (i.e., sulfolenoporphyrins) with benzoquinones and stilbenes, followed by aromatization, have been developed to load porphyrin with mixed annulation units (i.e., terphenyl and naphthoquinone), furnishing the low-symmetry pi-extended porphyrins (DxAy) with push-pull skeletons. All low-symmetrical chromophores display panchromatic absorption spectra, which look like a spectral combination of symmetrical congeners (D4/A4) in a certain ratio. Among them, tD2A2 with trans-arrangement of push/pull units possesses the largest maximum centered at 766 nm with the onset around 900 nm. The fusion of the electron-deficient naphthoquinone moiety on the porphyrin core results in the approximately quantitative regulation of the E-ox1 and HOMOs (i.e., 0.10-0.13 V increase for the E-ox1 and 0.14-0.16 eV decrease for the HOMOs per naphthoquinone unit). In brief, this work provides a new way to construct low-symmetry pi-extended porphyrins with tunable properties resorting to the ratios and locations of the annulated push-pull units.