文献类型：期刊文献

英文题名：Rational construction of perylenequinone annulated porphyrins via cycloaddition reactions

作者：Ma, Wenjing[1];Chen, Chen[1];Qin, Zhonghe[2];Zhu, Shuhui[1];Qiu, Ning[3];Baryshnikov, Glib[4];Li, Qizhao[1];Chengjie, Li[1];Liu, Xiujun[1]

机构：[1]East China Univ Sci & Technol, Frontiers Sci Ctr Materiobiol & Dynam Chem, Shanghai Key Lab Funct Mat Chem, Sch Chem & Mol Engn,Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]Univ Calif Irvine, Sch Phys Sci, Dept Chem, Irvine, CA 92697 USA;[3]Shanghai Starriver Bilingual Sch, 2588 Jindu Rd, Shanghai 201108, Peoples R China;[4]Linkoping Univ, Dept Sci & Technol, Lab Organ Elect, SE-60174 Norrkoping, Sweden

年份：2024

卷号：227

外文期刊名：DYES AND PIGMENTS

收录：;EI(收录号：20241715969557);WOS:【SCI-EXPANDED(收录号:WOS:001234703000001)】；

基金：This work was financially supported by the National Natural Science Foundation of China (22108078, 22131005, 22201074 and 22075077) , 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：Porphyrins; Perylene; Nitrile oxide; Diels-alder reaction; 3-dipolar cycloaddition; Assembly

摘要：Acenequinone-fused porphyrins show remarkable long wavelength absorption, low-lying LUMO orbital and uniform pi,pi-stacking, enabling the potential applications as opto-electronic materials and catalysts. At present, the synthesis of large quinone fused porphyrins remains challenging. To address this, the cycloaddition reactions of naphthoquinone-fused porphyrin (Ni4NQ), followed by oxidative aromatization, have been employed. Through Diels-Alder reaction with perylenes in the presence of chloranil, a series of perylenequinone-fused porphyrins (1Ni-4Ni) have been synthesized with an overall yield above 70 %. Later, the tri-adduct 3Ni underwent 1,3-dipolar cycloaddition with nitrile oxide and the following DDQ oxidation to outcome the unsymmetrical tetra-adduct 5Ni. Although the peripheral perylenequinones fusion in 1Ni-4Ni has limited impact on the absorption with respect to the naphthoquinone-fused counterpart Ni4NQ, introduction of an isoxazole via 1,3-cycloaddition (5Ni) leads to a bathochromic Q band. This result has been rationalized by theoretical calculations. Additionally, the incorporation of perylenequinone units gives rise to intense intermolecular pi,pi-stacking and CH-pi interactions within the crystal packing. The self-assembly behavior using a good/bad solvent strategy are structural dependence. The tri-perylenequinone-fused porphyrins 3Ni formed spherical architecture, while tetraperylenequinone-fused porphyrin 4Ni afforded cubic or petal-type assemblies.