一种包含反芳香性吡咯并[2,3-f]吲哚片段的双内消旋-α连接的N-稠合卟啉带银(III)配合物。

A Doubly meso-α Linked N-Confused Porphyrin Tape Silver(III) Complex Comprising an Antiaromatic Pyrrolo[2,3-f]indole Segment.

作者信息

Nakai Akito, Iwanaga Osamu, Tanaka Takayuki, Osuka Atsuhiro

机构信息

Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.

Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan.

出版信息

Chem Asian J. 2025 Jan 2;20(1):e202401144. doi: 10.1002/asia.202401144. Epub 2024 Nov 7.

DOI:10.1002/asia.202401144

PMID:39356174

Abstract

The free base form of doubly meso-α linked N-confused porphyrin (NCP) tape 3 was successfully synthesized via Ir(I) mediated intramolecular coupling. The following silver complexation afforded the Ag(III) complex of doubly meso-α linked NCP tape 4. While 3 exhibited 38π aromatic characters, 4 exhibited not only 18π aromatic NCP-type characteristics but also a decent antiaromatic contribution of 12π pyrrolo[2,3-f]indole segment, as probed by NMR spectra, absorption spectra, and DFT calculations.

摘要

通过铱（I）介导的分子内偶联成功合成了双间位-α连接的N-杂卟啉（NCP）带3的游离碱形式。随后的银络合反应得到了双间位-α连接的NCP带4的Ag（III）络合物。通过核磁共振光谱、吸收光谱和密度泛函理论计算表明，虽然3具有38π芳香特征，但4不仅具有18π芳香NCP型特征，还具有12π吡咯并[2,3-f]吲哚片段的适度反芳香贡献。