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Slow Magnetic Relaxations in Cobalt(II) Tetranitrate Complexes. Studies of Magnetic Anisotropy by Inelastic Neutron Scattering and High-Frequency and High-Field EPR Spectroscopy

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posted on 06.12.2016, 22:03 by Lei Chen, Hui-Hui Cui, Shelby E. Stavretis, Seth C. Hunter, Yi-Quan Zhang, Xue-Tai Chen, Yi-Chen Sun, Zhenxing Wang, You Song, Andrey A. Podlesnyak, Zhong-Wen Ouyang, Zi-Ling Xue
Three mononuclear cobalt­(II) tetranitrate complexes (A)2[Co­(NO3)4] with different countercations, Ph4P+ (1), MePh3P+ (2), and Ph4As+ (3), have been synthesized and studied by X-ray single-crystal diffraction, magnetic measurements, inelastic neutron scattering (INS), high-frequency and high-field EPR (HF-EPR) spectroscopy, and theoretical calculations. The X-ray diffraction studies reveal that the structure of the tetranitrate cobalt anion varies with the countercation. 1 and 2 exhibit highly irregular seven-coordinate geometries, while the central Co­(II) ion of 3 is in a distorted-dodecahedral configuration. The sole magnetic transition observed in the INS spectroscopy of 13 corresponds to the zero-field splitting (2­(D2 + 3E2)1/2) from 22.5(2) cm–1 in 1 to 26.6(3) cm–1 in 2 and 11.1(5) cm–1 in 3. The positive sign of the D value, and hence the easy-plane magnetic anisotropy, was demonstrated for 1 by INS studies under magnetic fields and HF-EPR spectroscopy. The combined analyses of INS and HF-EPR data yield the D values as +10.90(3), +12.74(3), and +4.50(3) cm–1 for 13, respectively. Frequency- and temperature-dependent alternating-current magnetic susceptibility measurements reveal the slow magnetization relaxation in 1 and 2 at an applied dc field of 600 Oe, which is a characteristic of field-induced single-molecule magnets (SMMs). The electronic structures and the origin of magnetic anisotropy of 13 were revealed by calculations at the CASPT2/NEVPT2 level.