The direct fusion of a diphenylmethane segment to a NiII5,10,15-triarylporphyrin with three linkages furnished an air- and moisture-stable neutral radical through unexpected and spontaneous oxidation. This radical was demetalated by treatment with H2SO4and CF3CO2H to provide the corresponding free-base radical. These porphyrin radicals are very stable owing to spin delocalization and have been fully characterized through UV/Vis/NIR absorption spectroscopy, X-ray crystallographic analysis, magnetic susceptibility measurements, electrochemical studies, laser-based ultrafast spectroscopic studies, and theoretical calculations. They were chemically oxidized and reduced to the corresponding cation and anion but did not react with hydrogen-atom donors.
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