meso‐Nitro‐ and meso‐Aminosubporphyrinatoboron(III)s and meso‐to‐meso Azosubporphyrinatoboron(III)s |
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| Authors: | Daiki Shimizu Seung‐Kyu Lee Prof. Dr. Dongho Kim Prof. Dr. Atsuhiro Osuka |
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| Affiliation: | 1. Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, Japan;2. Spectroscopy Laboratory for Functional π-Electronic, Systems and Department of Chemistry, Yonsei University, Seoul, Korea |
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| 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. |
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| Keywords: | azo compound charge transfer nitration porphyrinoid subporphyrin |
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