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Inorganics 2018, 6(2), 36; https://doi.org/10.3390/inorganics6020036

The Exploration and Analysis of the Magnetic Relaxation Behavior in Three Isostructural Cyano-Bridged 3d–4f Linear Heterotrinuclear Compounds

1
Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry-of-Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, China
2
Department of Chemistry and Beijing Key Laboratory of Energy Conversion and Storage Materials, Beijing Normal University, Beijing 100875, China
*
Authors to whom correspondence should be addressed.
Received: 23 January 2018 / Revised: 19 March 2018 / Accepted: 20 March 2018 / Published: 22 March 2018
(This article belongs to the Special Issue Single-Molecule Magnets)
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Abstract

Three isostructural cyano-bridged 3d–4f linear heterotrinuclear compounds, (H2.5O)4{Ln[TM(CN)5(CNH0.5)]2(HMPA)4} (Ln = YIII, TM = [FeIII]LS (1); Ln = DyIII, TM = [FeIII]LS (2); Ln = DyIII, TM = CoIII (3)), have been synthesized and characterized by single-crystal X-ray diffraction. Due to the steric effect of the HMPA ligands, the central lanthanide ions in these compounds possess a low coordination number, six-coordinate, exhibiting a coordination geometry of an axially elongated octahedron with a perfect D4h symmetry. Four HMPA ligands situate in the equatorial plane around the central lanthanide ions, and two [TM(CN)5(CNH0.5)]2.5− entities occupy the apical positions to form a cyano-bridged 3d–4f linear heterotrinuclear structure. The static magnetic analysis of the three compounds indicated a paramagnetic behavior of compounds 1 and 3, and possible small magnetic interactions between the intramolecular DyIII and [FeIII]LS ions in compound 2. Under zero dc field, the ac magnetic measurements on 2 and 3 revealed the in-phase component (χ′) of the ac susceptibility without frequency dependence and silent out-of-phase component (χ″), which was attributed to the QTM effect induced by the coordination geometry of an axially elongated octahedron for the DyIII ion. Even under a 1 kOe applied dc field, the χ″ components of 2 were revealed frequency dependence without peaks above 2 K. And under a 2 kOe and 3 kOe dc field, the χ″ components of 3 exhibited weak frequency dependence below 4 K with the absence of well-shaped peaks, which confirmed the poor single-ion magnetic relaxation behavior of the six-coordinate DyIII ion excluding any influence from the neighboring [FeIII]LS ions as that in the analogue 2. View Full-Text
Keywords: single-molecule magnets; single-ion magnets; lanthanide; coordination geometry single-molecule magnets; single-ion magnets; lanthanide; coordination geometry
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Xiong, X.; Liu, Y.; Li, S.; Xue, A.; Wang, J.; Zhang, C.; Zhu, W.; Sun, H. The Exploration and Analysis of the Magnetic Relaxation Behavior in Three Isostructural Cyano-Bridged 3d–4f Linear Heterotrinuclear Compounds. Inorganics 2018, 6, 36.

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