meso-Nitro- and meso-Aminosubporphyrinatoboron(III)s and meso-to-meso Azosubporphyrinatoboron(III)s

Daiki Shimizu; Seung-Kyu Lee; Dongho Kim; Atsuhiro Osuka

doi:10.1002/asia.201601019

meso-Nitro- and meso-Aminosubporphyrinatoboron(III)s and meso-to-meso Azosubporphyrinatoboron(III)s

Chem Asian J. 2016 Oct 20;11(20):2946-2952. doi: 10.1002/asia.201601019. Epub 2016 Sep 14.

Authors

Daiki Shimizu¹, Seung-Kyu Lee², Dongho Kim³, Atsuhiro Osuka⁴

Affiliations

¹ Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.
² Spectroscopy Laboratory for Functional π-Electronic, Systems and Department of Chemistry, Yonsei University, Seoul, 03722, Korea.
³ Spectroscopy Laboratory for Functional π-Electronic, Systems and Department of Chemistry, Yonsei University, Seoul, 03722, Korea. dongho@yonsei.ac.kr.
⁴ Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan. osuka@kuchem.kyoto-u.ac.jp.

PMID: 27529407
DOI: 10.1002/asia.201601019

Abstract

meso-Nitrosubporphyrinatoboron(III) was synthesized by nitration of meso-free subporphyrin with AgNO₂ /I₂ . The subsequent reduction with a combination of NaBH₄ and Pd/C gave meso-aminosubporphyrinatoboron(III). meso-Nitro- and meso-amino-groups significantly influenced the electronic properties of subporphyrin, which has been confirmed by NMR and UV/Vis spectra, electrochemical analysis, and DFT calculations. Oxidation of meso-aminosubporphyrinatoboron(III)s with PbO₂ cleanly gave meso-to-meso azosubporphyrinatoboron(III)s that exhibited almost coplanar conformations and large electronic interaction through the azo-bridge.

Keywords: azo compound; charge transfer; nitration; porphyrinoid; subporphyrin.