Strong intramolecular ferromagnetic couplings in nickel(II) and copper(II) complexes chelated with tert-butyl 5-methoxy-2-pyridyl nitroxide |
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| Authors: | Atsushi Okazawa Takashi Nogami Takayuki Ishida |
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| Affiliation: | Department of Applied Physics and Chemistry, The University of Electro-Communications, Chofu, Tokyo 182-8585, Japan;Department of Chemistry, University of Florida, Gainesville, FL, USA |
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| Abstract: | We successfully isolated a new paramagnetic bidentate ligand tert-butyl 5-methoxy-2-pyridyl nitroxide (meopyNO). Complexation of nickel(II) and copper(II) perchlorates with meopyNO gave the corresponding ML2-type bis-chelated compounds. The magnetic studies showed that they were ground high-spin molecules with 2J/kB = +288(5) and +178(3) K for [M(meopyNO)2(H2O)2] · (ClO4)2 (M = Ni and Cu, respectively), where the spin Hamiltonian is defined as H = ?2J(S1 · S2 + S2 · S3). From the crystallographic analysis, the torsion angles (?) around M–O–N–C2py were 4.2(3)° and 6.87(19)°, respectively, being so small that the orthogonality between the magnetic radical π1 and the metal dσ orbitals would be guaranteed. |
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