Chemistry - A European Journal
Chemistry - A European Journal
5 years ago

Stable NiII Porphyrin meso-Oxy Radical with a Quartet Ground State

Stable NiII Porphyrin meso-Oxy Radical with a Quartet Ground State
Daiki Shimizu, Atsuhiro Osuka, Cosima Stähler, Kota Yoshida, Ko Furukawa, Rainer Herges
10,15,20-Tris(pentafluorophenyl)-substituted NiII–porphyrin meso-oxy radical bearing two coordinating pyridines was synthesized as a stable radical with a quartet ground state (S=3/2). X-ray structural analysis revealed that the NiII porphyrin moiety is fairly planar and the Ni−N bond lengths are considerably longer, indicating the high-spin state of the NiII center. The radical exhibited a quartet ground state, indicating the ferromagnetic interaction between the high-spin NiII center (S=1) and the porphyrin meso-oxy radical (S=1/2). Hexagonally coordinated NiII complex with 10,15–20-triarylporphyrin meso-oxy radical and two pyridines as ligands was synthesized. The complex exhibited a S=3/2 ground state with large doublet-quartet energy gap due to ferromagnetic interaction between the high-spin NiII center (S=1) and the porphyrin meso-oxy radical (S=1/2). Its structure, as well as optical, magnetic, and electrochemical properties have been fully characterized (see figure).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201701354

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