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The effect of the electronic structure and flexibility of the counteranions on magnetization relaxation in [Dy(L)2(H2O)5]3+ (L = phosphine oxide derivative) pentagonal bipyramidal SIMs

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Abstract

We report here a new DyIII-SIM [Dy(OPCy3)2(H2O)5](CF3SO3)3·2OPCy3 (OPCy3 = tricyclohexylphosphine oxide) with a pentagonal bipyramidal geometry, which exhibits a blocking temperature TB = 8.5 K and an anisotropy barrier Ueff = 562 K. Ab initio calculations show that this complex exhibits the largest Ucalc = 732 K among the DyIII-SIM complexes containing the [Dy(L)2(H2O)5]3+ (L = phosphine oxide derivative) cationic unit, which is essentially due to the electronic effects of the triflate anion that increase the charge difference between the oxygen atoms of the ligands L coordinated in axial positions and those belonging to the equatorial water molecules. This charge difference enhancement, which is also reflected in a larger difference between the corresponding Dy–O distances (Δ), appears to be the driving force to increase the Ucalc value. The comparatively smaller experimental Ueff value observed for this compound has been justified by the flexibility of the structural network due to the size of the triflate counteranions. The absence of a clear correlation between TB and Ueff (or Ucalc) suggests the involvement of Raman and QTM mechanisms in the magnetization relaxation process.

Graphical abstract: The effect of the electronic structure and flexibility of the counteranions on magnetization relaxation in [Dy(L)2(H2O)5]3+ (L = phosphine oxide derivative) pentagonal bipyramidal SIMs

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Publication details

The article was received on 30 Oct 2019, accepted on 01 Dec 2019 and first published on 02 Dec 2019


Article type: Research Article
DOI: 10.1039/C9QI01412H
Inorg. Chem. Front., 2020, Advance Article

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    The effect of the electronic structure and flexibility of the counteranions on magnetization relaxation in [Dy(L)2(H2O)5]3+ (L = phosphine oxide derivative) pentagonal bipyramidal SIMs

    I. F. Díaz-Ortega, J. M. Herrera, S. Dey, H. Nojiri, G. Rajaraman and E. Colacio, Inorg. Chem. Front., 2020, Advance Article , DOI: 10.1039/C9QI01412H

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