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

Ismael F. Diáz-Ortega, Juan Manuel Herrera, Sourav Dey, Hiroyuki Nojiri, Gopalan Rajaraman, Enrique Colacio

Research output: Contribution to journalArticlepeer-review

4 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)689-699
Number of pages11
JournalInorganic Chemistry Frontiers
Volume7
Issue number3
DOIs
Publication statusPublished - 2020 Feb 7

ASJC Scopus subject areas

  • Inorganic Chemistry

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