A Quadruply Bridged Non‐Offset Face‐to‐Face Porphyrin Dimer and Cross‐Shaped Pentameric Porphyrin Tapes Based on 2,7,12,17‐Tetrakis(pinacolatoboryl) Ni(II) Porphyrin
A Quadruply Bridged Non‐Offset Face‐to‐Face Porphyrin Dimer and Cross‐Shaped Pentameric Porphyrin Tapes Based on 2,7,12,17‐Tetrakis(pinacolatoboryl) Ni(II) Porphyrin
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基于2,7,12,17-四(频哪醇硼基)Ni(II)卟啉的四桥非偏移面对面卟啉二聚体和十字形五聚卟啉带
DOI：
10.1002/anie.202300260
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Song Jianxin
中科院分区：
文献类型：
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作者：
Ye Meng;Deng Fangling;Xu Ling;Rao Yutao;Yin Bangshao;Zhou Mingbo;Kurosaki Ryo;Aratani Naoki;Osuka Atsuhiro;Song Jianxin
2，7，12，17-四（频哪醇合硼基）镍卟啉5 Ni通过铱催化的卟啉硼基化反应和镍金属化反应以75%的产率合成，并且已被证明是有用的合成子，得到2，7，12，17-四芳基化镍卟啉6 a-d、外围八芳基化镍卟啉8 a-d、四重桥连的面对面非偏移镍卟啉二聚体12和十字形β-meso单连接卟啉五聚体和九聚体。氧化十字形β-中位单连接的卟啉五聚体14 Ni和14 Zn得到稠合五聚体带15 Ni和15 Zn。X射线衍射分析揭示了12、14 Zn和15 Ni的结构。对12进行了光学分离，得到了激子耦合蓝移Soret带的双信号耦合模式。五聚体卟啉带15 Zn在1156 nm处显示出红移的吸收带和七个可逆的氧化还原波。
2,7,12,17‐Tetrakis(pinacolatoboryl) NiIIporphyrin5 Niwas synthesized in 75 % yield by Ir‐catalyzed borylation of porphine followed by NiIImetalation and has been demonstrated to be a useful synthon, giving 2,7,12,17‐tetraaryated NiIIporphyrins6 a–d, peripherally octaarylated NiIIporphyrins8 a–d, quadruply bridged face‐to‐face non‐offset NiII‐porphyrin dimer12, and cross‐shapedβ‐mesosingly linked porphyrin pentamers and nonamers. Oxidation of cross‐shapedβ‐mesosingly linked porphyrin pentamers14 Niand14 Zngave fused pentameric tapes15 Niand15 Zn. The structures of12,14 Zn, and15 Nihave been revealed by X‐ray diffraction analysis. Optical separation of12has been accomplished, showing a bisignate coupling pattern for exciton‐coupled blue‐shifted Soret band. Pentameric porphyrin tape15 Znexhibits a red‐shifted absorption band at 1156 nm and seven reversible redox waves.