title: meso-Nitro- and meso-Aminosubporphyrinatoboron(III)s and meso-to-meso Azosubporphyrinatoboron(III)s.
abstract: meso-Nitrosubporphyrinatoboron(III) was synthesized by nitration of meso-free subporphyrin with AgNO2/I2. The subsequent reduction with a combination of NaBH4and 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 PbO2cleanly gave meso-to-meso azosubporphyrinatoboron(III)s that exhibited almost coplanar conformations and large electronic interaction through the azo-bridge.
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.
authors.forename: Daiki
authors.initials: D
authors.lastname: Shimizu
authors.affiliation: Spectroscopy Laboratory for Functional π-Electronic, Systems and Department of Chemistry, Yonsei University, Seoul, 03722, Korea.
authors.forename: Seung-Kyu
authors.initials: SK
authors.lastname: Lee
authors.affiliation: Spectroscopy Laboratory for Functional π-Electronic, Systems and Department of Chemistry, Yonsei University, Seoul, 03722, Korea. dongho@yonsei.ac.kr.
authors.forename: Dongho
authors.initials: D
authors.lastname: Kim
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan. osuka@kuchem.kyoto-u.ac.jp.
authors.forename: Atsuhiro
authors.initials: A
authors.lastname: Osuka
keywords: azo compound; charge transfer; nitration; porphyrinoid; subporphyrin