Tetrabromo[36]octaphyrin: A Promising Precursor of Directly Fused Porphyrin(2.1.1.1) Dimer and meso-α Fused N-Confused Porphyrin Dimer
Tetrabromo[36]octaphyrin: A Promising Precursor of Directly Fused Porphyrin(2.1.1.1) Dimer and meso-α Fused N-Confused Porphyrin Dimer
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DOI：
10.1002/anie.202112023
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发表时间：
2021-11-09
影响因子：
16.6
通讯作者：
Osuka, Atsuhiro
中科院分区：
文献类型：
--
作者：
Nakai, Akito;Kim, Jinseok;Osuka, Atsuhiro
3，7，23，27-四溴[36]八卟啉2是一种新型的八卟啉化合物，具有两个meso自由位置。令人惊讶的是，其Zn-II和Ni-II络合反应通过跨环C-C键形成分别产生直接稠合的卟啉（2.1.1.1）二聚体6和内消旋-α稠合的N-混杂卟啉（NCP）二聚体7，作为NCP带的第一个实例。虽然6由于整体36 π莫比乌斯芳香性而表现出diatropic环电流效应，但7由于整体Huckel 36 π反芳香性而表现出paratropic环电流效应。此外，7与PbO 2的氧化允许形成其两个电子的氧化物种9，表现出diatropic环电流效应，由于全球休克尔34 π芳香性。这项工作表明，无介孔大膨胀卟啉可以是一个有前途的平台，以产生新的融合卟啉。
3,7,23,27-Tetrabromo[36]octaphyrin 2 was synthesized as a novel octaphyrin bearing two meso-free positions. Surprisingly, its Zn-II and Ni-II complexation reactions produced a directly fused porphyrin(2.1.1.1) dimer 6, and a meso-alpha fused N-confused porphyrin (NCP) dimer 7, as the first example of NCP tape, respectively, via transannular C-C bond formation. While 6 exhibits a diatropic ring-current effect owing to the global 36 pi Mobius aromaticity, 7 shows a paratropic ring-current effect due to the global Huckel 36 pi antiaromaticity. In addition, the oxidation of 7 with PbO2 allowed for formation of its two-electron oxidized species 9 that exhibited a diatropic ring-current effect due to the global Huckel 34 pi aromaticity. This work has demonstrated that meso-free large expanded porphyrins can be a promising platform to produce novel fused porphyrinoids.