文献类型：期刊文献

英文题名：Anthraquinone fused sulfolenoporphyrins: Regulation of reactivity and property through annulations

作者：Lin, Qianghao[1];Ma, Wenjing[1];Yu, Yichen[2];Tang, Yuqiu[1];Mo, Wenyang[1];Li, Chengjie[1];Li, Qizhao[1];Li, Yuxin[3];Liu, Xiujun[1]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai Key Lab Funct Mat Chem, Shanghai 200237, Peoples R China;[2]Imperial Coll London, Dept Chem, London SW7 2AZ, England;[3]Heilongjiang Univ, Sch Chem & Mat Sci, Key Lab Funct Inorgan Mat Chem MOE, Harbin 150080, Peoples R China

年份：2024

卷号：28

期号：04

起止页码：243

外文期刊名：JOURNAL OF PORPHYRINS AND PHTHALOCYANINES

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001216902300002)】；

基金：This work was financially supported by the National Natural Science Foundation of China (22108078, 22075077, 22131005 and 22201074,), Natural Science Foundation of Shanghai (23ZR1415600, 22ZR1416100), Shanghai Rising-Star Program (23QA1402100) and the Fundamental Research Funds for the Central Universities.

语种：英文

外文关键词：Sulfolenoporphyrin; Diels-Alder reaction; Annulation; Structure-Reactivity

摘要：The sulfolenoporphyrin-based Diels-Alder reaction is an efficient strategy in the construction of aromatic ring-fused porphyrins. However, the structure-reactivity relationship is still less explored. Here, we have synthesized the mono-, bis- and tri-anthraquinone fused sulfolenoporphyrins and explore the effect of anthraquinone fusion on their further Diels-Alder reactions. As a result, more anthraquinone fusions lead to higher reactivity but lower annulation yield. Theoretical calculation discloses that anthraquinone fusion has the HOMO of the dienes (i.e., the intermediates after extrusion of SO2 from sulfolenoporphyrins) raised owing to the pi-extension, affording high reactivity. However, as the number of ring fusions increases, the LUMO energy levels of dienes are reduced, which seems to benefit the side reaction (i.e., the dimer/oligomerization owing to the Diels-Alder reaction among porphyrin dienes), leading to the rapid consumption of dienes and low yields. Besides, the influence of the peripheral anthraquinone units on molecular stacking, absorption as well as aromaticity was investigated experimentally and computationally. In brief, this work has investigated the structure-reactivity relationship of sulfolenoporphyrins in the Dies-Alder reaction, which will help construct pi-extended porphyrin rationally.