Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, 565-0871, Japan.
Chemistry. 2019 Feb 1;25(7):1711-1715. doi: 10.1002/chem.201805659. Epub 2019 Jan 9.
Oxidation of β-to-β directly linked and sulfur-bridged meso-amino Ni -porphyrin dimers with PbO gave helical tetrapyrrin (biliverdin analogue)-fused Ni -porphyrins. These ring cleaving reactions differ markedly from the previously reported oxidation of a β-β linked Ni -porphyrin dimer carrying one amino group, which gave an azepine-fused porphyrin dimer. The tetrapyrrin-fused Ni -porphyrins display intense NIR absorption bands at 1200-1400 nm and reversible redox processes because of the highly π-conjugated networks and rigid structures. These tetrapyrrin-fused Ni -porphyrins were separated to stable enantiomers, which showed clear Cotton effects in their CD spectra with Δϵ of 10 order.
用 PbO 直接氧化β-到-β连接且硫桥联的间位氨基 Ni-卟啉二聚体，得到了螺旋四吡咯（胆绿素类似物）-桥联的 Ni-卟啉。这些环裂解反应与之前报道的β-连接的 Ni-卟啉二聚体的氧化反应明显不同，该反应带有一个氨基，得到了氮杂卓桥联的卟啉二聚体。四吡咯桥联的 Ni-卟啉由于具有高度的π共轭网络和刚性结构，在 1200-1400nm 处显示出强烈的近红外吸收带和可逆的氧化还原过程。这些四吡咯桥联的 Ni-卟啉被分离成稳定的对映体，其圆二色谱（CD 谱）中显示出明显的 Cotton 效应，Δϵ 值为 10 阶。
