Internally Bridged Huckel Aromatic [46]Decaphyrins: (Doubly‐Twisted‐Annuleno)Doubly‐Twisted‐Annulene Variants

Internally Bridged Huckel Aromatic [46]Decaphyrins: (Doubly‐Twisted‐Annuleno)Doubly‐Twisted‐Annulene Variants
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内桥 Huckel 芳香族 [46]十菲林:(双扭曲环烯)双扭曲环烯变体

DOI:
10.1002/chem.201900819
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发表时间:
2019
期刊:
Chemistry - A European Journal
影响因子:
--
通讯作者:
Osuka Atsuhiro
Osuka Atsuhiro
中科院分区:
--
文献类型:
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作者:
Soya Takanori;Osuka Atsuhiro

文献摘要

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在内部合成了3,3‘-联苯基,2,2’,5,5‘-联噻吩基和2,5-硫代[3,2-b]噻吩桥联的[46]十氢呋喃。2,2‘,5,5’-联噻吩桥联的[46]噻吩环上的[32]七氢吡喃和[30]六氢呋喃中的内核修饰的[32]七氢吡喃和[30]六氢呋喃除具有全局46个(doubly‐twisted‐annuleno)doubly‐twisted‐annulene共轭环外,还具有双扭曲的拓扑结构(|lk|=2),被认为是π的变体。由于全球46个π电子网络的作用,所有这些脱氢反应都表现出明显的Hückel芳香性,但由于桥的垂直取向,局部半电路的贡献几乎可以忽略不计。
Internally 3,3′‐biphenyl‐, 2,2′,5,5′‐bithiophene‐, and 2,5‐thieno[3,2‐b]thiophene‐bridged [46]decaphyrins were prepared. In addition to the global 46π‐conjugated circuits, the internal core‐modified [32]heptaphyrin‐ and [30]hexaphyrin moieties in 2,2′,5,5′‐bithiophene‐ and 2,5‐thieno[3,2‐b]thiophene‐bridged [46]decaphyrins also possess doubly twisted topologies (|Lk|=2) and are regarded as (doubly‐twisted‐annuleno)doubly‐twisted‐annulene variants. All these decaphyrins display distinct Hückel aromaticity owing to the global 46π‐electronic networks but the contributions of the local half circuits were almost negligible due to the perpendicular orientation of the bridges.