文献类型：期刊文献

英文题名：Rational Constructions 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]; Li, Chengjie[1]; Liu, Xiujun[1]

机构：[1] Key Laboratory for Advanced Materials, Shanghai Key Laboratory of Functional Materials Chemistry, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry & Molecular Engineering, East China University of Science & Technology, Shanghai, 200237, China; [2] Department of Chemistry, School of Physical Sciences, University of California, Irvine, CA, 92697, United States; [3] Shanghai Starriver Bilingual School, No. 2588, Jindu Road, Shanghai, 201108, China; [4] Bohdan Khmelnytsky National University of Cherkasy, Ukraine

年份：2024

外文期刊名：SSRN

收录：EI(收录号：20240097046)

语种：英文

外文关键词：Cycloaddition - Ketones - Nitrogen oxides - Quinone - Red Shift

摘要：Acenequinone-fused porphyrins show remarkable longwavelength absorption, low-lying LUMO orbital and uniform π,π-stacking, enabling the ultilization in organic electronics. At present, the synthesis of large quinone fused porphyrins remains challenging. To address this, the Diels-Alder and 1,3-dipolar cycloaddition reactions of naphthoquinone-fused porphyrin, followed by aromatization, have been explored1. As a result, this strategy effectively facilitates the construction of the perylenequinone-fused porphyrins with an overall yield above 70%. Despite, expanding the peripheral quinone units has a limited impact on the absorption with respect to the naphthoquinone-fused counterpart, introducing isoxazole via 1,3-cycloaddition leads to an unsymmetrical skeleton and a red-shifted Q band. This result has been rationalized by theoretical predictions regarding the frontier orbitals. Additionally, the incorporation of perylenequinone units gives rise to intense intermolecular π,π-stacking, and numerous CH-π interactions within the crystal packing. Further investigation on the self-assembly behavior using a good/bad solvent strategy revealed structural dependence. The tri-perylenequinone-fused porphyrins 3Ni formed spherical architecture, while tetraperylenequinone-fused porphyrin 4Ni afforded small cubic or petal-type assemblies. ? 2024, The Authors. All rights reserved.