Bis-palladium(II) complex of doubly N-confused octaphyrin(1.1.1.1.1.1.1.1): Mobius aromaticity and chiroptical properties
Bis-palladium(II) complex of doubly N-confused octaphyrin(1.1.1.1.1.1.1.1): Mobius aromaticity and chiroptical properties
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双N-混淆八菲林的双钯(II)络合物(1.1.1.1.1.1.1.1)：莫比乌斯芳香性和手性光学性质
DOI：
10.1142/s1088424619501116
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发表时间：
2020
影响因子：
1.5
通讯作者：
Furuta Hiroyuki
中科院分区：
文献类型：
--
作者：
Basumatary Biju;Mitsuno Koki;Ishida Masatoshi;Furuta Hiroyuki
合成并表征了一种具有Möbius扭曲拓扑结构的双N-混乱八卟啉（Pd-2）双钯（II）配合物。由于在莫比乌斯扭曲的octaphyrin支架上有效的36电子离域，在近红外（NIR）区域观察到特征Soret和类Q吸收特征。然而，配合物Pd-2表现出弱的芳香性，这归因于1H NMR化学位移和理论评估（核独立化学位移（NICS））中明显的交叉共轭共振贡献。由于双钯络合双N-混乱八氢卟啉2赋予了显著的构象稳定性，因此Pd-2的拓扑手性对映体以（-和（-扭曲形式被成功分离。所得异构体显示出相对较大的圆二色性（CD）响应，在近红外区（823 nm）的吸收各向异性因子为0.009。此外，Pd-2的循环伏安图显示了其大共轭体系的富氧化还原性质。
A novel bis-palladium(II) complex of doubly N-confused octaphyrin (Pd-2) adopting a Möbius-twisted topological structure was synthesized and characterized. Due to the effective 36-electronic delocalization over the Möbius-twisted octaphyrin scaffold, characteristic Soret and Q-like absorption features were observed in the near-infrared (NIR) region. However, the complexPd-2exhibited weak aromatic character attributed to the distinct cross-conjugated resonance contribution as inferred from the1H NMR chemical shifts as well as theoretical assessments (nucleus-independent chemical shift (NICS)). Since the bis-palladium(II) complexation of doubly N-confused octaphyrin2imparted significant conformational stability, topologically chiral enantiomers ofPd-2were successfully separated as (- and (-twisted forms. The resulting isomers revealed relatively large circular dichroism (CD) responses with an absorption anisotropy factor of0.009 in the NIR region (823 nm). In addition, the cyclic voltammogram ofPd-2revealed redox-rich properties due to its large-conjugated system.