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Mechanism of Magnetization Relaxation in {MIII2DyIII2} (M = Cr, Mn, Fe, Al) “Butterfly” Complexes: How Important Are the Transition Metal Ions Here?

Abstract

We describe the synthesis, characterisation and magnetic studies of four tetranuclear, isostructural “butterfly” heterometallic complexes: [MIII2LnIII2(μ3-OH)2(p-Me-PhCO2)6(L)2] (H2L = 2,2'-((pyridin-2-ylmethyl)azanediyl)bis(ethan-1-ol), M = Cr, Ln = Dy (1), Y (2), M = Mn, Ln = Dy (3), Y (4)), which extend our previous study on the analogous 5 {Fe2Dy2}, 6 {Fe2Y2}and 7{Al2Dy2} compounds. We also present data on the yttrium diluted 7 {Al2Dy2}: 8 {Al2Dy0.18Y1.82}. Dc and ac magnetic susceptibility data reveal single-molecule magnet (SMM) behaviour for complex 3 {Mn2Dy2}, in the absence of an external magnetic field, with an anisotropy barrier Ueff of 19.2 K, while complex 1 {Cr2Dy2}, shows no ac signals even under applied dc field, indicating absence of SMM behaviour. The diluted sample 8 {Al2Dy0.18Y1.82} shows field induced SMM behaviour with an anisotropy barrier Ueff of 69.3K. Furthermore, the theoretical magnetic properties of [MIII2LnIII2(μ3-OH)2(p-Me-PhCO2)6(L)2] (M = Cr, 1 or Mn, 3) and their isostructural complexes: [MIII2DyIII2(μ3-OH)2(p-Me-PhCO2)6(L)2] (M = Fe, 5 or Al, 7) are discussed and compared. To understand the experimental observations for this family, DFT and ab initio CASSCF+RASSI-SO calculations were performed. The experimental and theoretical calculations suggest that altering the 3dIII ions can affect the single-ion properties and the nature and the magnitude of the 3dIII-3dIII, 3dIII-DyIII and DyIII−DyIII magnetic coupling, thus quenching the quantum tunneling of magnetisation (QTM) significantly, thereby improving the SMM properties within this motif. This is the first systematic study looking at variation and therefore role of trivalent transition metal ions, as well as the diamgnetic AlIII ion,on slow relaxation of magnetisation within a series of isostructural 3d-4f butterfly compounds.

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Publication details

The article was received on 30 Nov 2018, accepted on 04 Apr 2019 and first published on 16 Apr 2019


Article type: Edge Article
DOI: 10.1039/C8SC05362F
Citation: Chem. Sci., 2019, Accepted Manuscript
  • Open access: Creative Commons BY-NC license
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    Mechanism of Magnetization Relaxation in {MIII2DyIII2} (M = Cr, Mn, Fe, Al) “Butterfly” Complexes: How Important Are the Transition Metal Ions Here?

    Y. Peng, M. K. Singh, V. Mereacre, C. Anson, G. Rajaraman and A. K. Powell, Chem. Sci., 2019, Accepted Manuscript , DOI: 10.1039/C8SC05362F

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