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Porphyrindiene-Based Tandem Diels–Alder Reaction for Preparing Low-Symmetry π-Extended Porphyrins with Push–Pull Skeletons
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2022-06-24 , DOI: 10.1021/acs.joc.2c00699 Guanyue Cao 1 , Glib Baryshnikov 2 , Chen Chen 1 , Liyuan Chen 1 , Tengjiao Zhao 1 , Shuyi Fu 1 , Zhenhui Jiang 1 , Xiujun Liu 1 , Qizhao Li 1 , Yongshu Xie 1 , Chengjie Li 1
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2022-06-24 , DOI: 10.1021/acs.joc.2c00699 Guanyue Cao 1 , Glib Baryshnikov 2 , Chen Chen 1 , Liyuan Chen 1 , Tengjiao Zhao 1 , Shuyi Fu 1 , Zhenhui Jiang 1 , Xiujun Liu 1 , Qizhao Li 1 , Yongshu Xie 1 , Chengjie Li 1
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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 π-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 Eox1 and HOMOs (i.e., 0.10–0.13 V increase for the Eox1 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 π-extended porphyrins with tunable properties resorting to the ratios and locations of the annulated push–pull units.
中文翻译：
基于卟啉二烯的串联 Diels-Alder 反应制备具有推拉骨架的低对称 π-扩展卟啉
掩蔽的卟啉二烯（即硫代卟啉）与苯醌和二苯乙烯的串联 Diels-Alder 反应，随后芳构化，已被开发用于负载具有混合环单元（即三联苯和萘醌）的卟啉，从而提供低对称 π 扩展卟啉（DxAy ) 与推拉骨架。所有低对称发色团都显示全色吸收光谱，看起来像是对称同源物（D4 / A4）以一定比例的光谱组合。其中，tD2A2具有推/拉单元的反式排列具有最大的最大值，以 766 nm 为中心，在 900 nm 附近开始。卟啉核心上缺电子萘醌部分的融合导致E ox1和 HOMOs 的近似定量调节（即，每个萘醌单元的E ox1增加 0.10-0.13 V ，HOMOs 减少 0.14-0.16 eV） . 简而言之，这项工作提供了一种新的方法来构建具有可调特性的低对称 π 扩展卟啉，这取决于环形推挽单元的比率和位置。
更新日期：2022-06-24
中文翻译：
基于卟啉二烯的串联 Diels-Alder 反应制备具有推拉骨架的低对称 π-扩展卟啉
掩蔽的卟啉二烯（即硫代卟啉）与苯醌和二苯乙烯的串联 Diels-Alder 反应，随后芳构化，已被开发用于负载具有混合环单元（即三联苯和萘醌）的卟啉，从而提供低对称 π 扩展卟啉（DxAy ) 与推拉骨架。所有低对称发色团都显示全色吸收光谱，看起来像是对称同源物（D4 / A4）以一定比例的光谱组合。其中，tD2A2具有推/拉单元的反式排列具有最大的最大值，以 766 nm 为中心，在 900 nm 附近开始。卟啉核心上缺电子萘醌部分的融合导致E ox1和 HOMOs 的近似定量调节（即，每个萘醌单元的E ox1增加 0.10-0.13 V ，HOMOs 减少 0.14-0.16 eV） . 简而言之，这项工作提供了一种新的方法来构建具有可调特性的低对称 π 扩展卟啉，这取决于环形推挽单元的比率和位置。
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