Please use this identifier to cite or link to this item: https://doi.org/10.1021/ic302568x
Title: Interplay of Strongly Anisotropic Metal Ions in Magnetic Blocking of Complexes
Authors: Ungur, Liviu 
Thewissen, Maarten
Costes, Jean-Pierre
Wernsdorfer, Wolfgang
Chibotaru, Liviu F
Keywords: Science & Technology
Physical Sciences
Chemistry, Inorganic & Nuclear
Chemistry
2ND-ORDER PERTURBATION-THEORY
SINGLE-MOLECULE MAGNETS
TB
RELAXATION
DY
EXCHANGE
FAMILY
GD
HO
LN
Issue Date: 3-Jun-2013
Publisher: AMER CHEMICAL SOC
Citation: Ungur, Liviu, Thewissen, Maarten, Costes, Jean-Pierre, Wernsdorfer, Wolfgang, Chibotaru, Liviu F (2013-06-03). Interplay of Strongly Anisotropic Metal Ions in Magnetic Blocking of Complexes. INORGANIC CHEMISTRY 52 (11) : 6328-6337. ScholarBank@NUS Repository. https://doi.org/10.1021/ic302568x
Abstract: The key characteristic of single-molecule magnets (SMMs) is the anisotropy-induced blocking barrier, which should be as efficient as possible, i.e., to be able to provide long magnetic relaxation times at elevated temperatures. The strategy for the design of efficient SMMs on the basis of transition-metal complexes such as Mn12Ac is well established, which is not the case of complexes involving strongly anisotropic metal ions such as cobalt(II) and lanthanides (Ln). While strong intraionic anisotropy in the latter allows them to block the magnetization already in mononuclear complexes, the presence of several such ions in a complex does not result automatically in more efficient SMMs. Here, the magnetic blocking in the series of isostructural 3d-4f complexes CoII-LnIII-CoII, Ln = Gd, Tb, and Dy, is analyzed using an originally developed ab initio based approach for the investigation of blocking barriers. The theoretical analysis allows one to explain the counterintuitive result that the Co-Gd-Co complex is a better SMM than terbium and dysprosium analogues. It turns out that the highly efficient magnetic blockage in the Co-Gd-Co complex results from a concomitant effect of unexpectedly large unquenched orbital momentum on CoII ions (ca. 1.7 μB) and the large spin on the gadolinium (S = 7/2), which provides a multilevel blocking barrier, similar to the one of the classical Mn12Ac. We conclude that efficient SMMs could be obtained in complexes combining strongly anisotropic and isotropic metal ions with large angular momentum rather than in polynuclear compounds involving strongly anisotropic ions only. © 2013 American Chemical Society.
Source Title: INORGANIC CHEMISTRY
URI: https://scholarbank.nus.edu.sg/handle/10635/228845
ISSN: 00201669
1520510X
DOI: 10.1021/ic302568x
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