Porphyrindiene-Based Tandem Diels-Alder Reaction for Preparing Low-Symmetry pi-Extended Porphyrins with Push-Pull Skeletons

Funding Agencies|National Natural Science Foundation of China [NSFC 22075077, 22131005, 22108078, 21971063]; Natural Science Foundation of Shanghai [20ZR1414100, 22ZR1416100]; Program of Shanghai Academic Research Leader [20XD1401400]; Fundamental Research Funds for the Central Universities
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.

Baryshnikov, GlibLinköpings universitet,Laboratoriet för organisk elektronik,Tekniska fakulteten(Swepub:liu)gliba58 (författare)
Chen, ChenEast China Univ Sci & Technol, Peoples R China (författare)
Chen, LiyuanEast China Univ Sci & Technol, Peoples R China (författare)
Zhao, TengjiaoEast China Univ Sci & Technol, Peoples R China (författare)
Fu, ShuyiEast China Univ Sci & Technol, Peoples R China (författare)
Jiang, ZhenhuiEast China Univ Sci & Technol, Peoples R China (författare)
Liu, XiujunEast China Univ Sci & Technol, Peoples R China (författare)
Li, QizhaoEast China Univ Sci & Technol, Peoples R China (författare)
Xie, YongshuEast China Univ Sci & Technol, Peoples R China (författare)
Li, ChengjieEast China Univ Sci & Technol, Peoples R China (författare)
East China Univ Sci & Technol, Peoples R ChinaLaboratoriet för organisk elektronik (creator_code:org_t)

Ingår i:Journal of Organic Chemistry: AMER CHEMICAL SOC87:14, s. 9001-90100022-32631520-6904

Av författaren/redakt...: Cao, Guanyue; Baryshnikov, Gli ...; Chen, Chen; Chen, Liyuan; Zhao, Tengjiao; Fu, Shuyi; visa fler...; Jiang, Zhenhui; Liu, Xiujun; Li, Qizhao; Xie, Yongshu; Li, Chengjie; visa färre...

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