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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• 作者：Lei Chen ; Hui-Hui Cui ; Shelby E. Stavretis ; Seth C. Hunter ; Yi-Quan Zhang ; Xue-Tai ChenYi-Chen Sun ; Zhenxing Wang ; You Song ; Andrey A. Podlesnyak ; Zhong-Wen Ouyang ; Zi-Ling Xue
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：December 19, 2016
• 年：2016
• 卷：55
• 期：24
• 页码：12603-12617
• 全文大小：826K
• ISSN：1520-510X

文摘

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 1–3 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 1–3, 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 1–3 were revealed by calculations at the CASPT2/NEVPT2 level.