Magnetic properties and magnetocaloric effect of Ln = Dy, Tb carborane-based metal–organic frameworks

Abstract

We present the synthesis and magneto-thermal properties of carborane-based lanthanide metal–organic frameworks (MOFs) with the formula {[(Ln)₃(mCB-L)₄(NO₃)(DMF)_n]·Solv}, where Ln = Dy or Tb, characterized by dc and ac susceptibility, X-ray absorption spectroscopy (XAS), X-ray magnetic circular dichroism (XMCD) and heat capacity measurements. The MOF structure is formed by polymeric 1D chains of Ln ions with three different coordination environments (Ln1, Ln2, Ln3) running along the b-axis, linked by carborane-based linkers thus to provide a 3D structure. Static magnetic measurements reveal that these MOFs behave at low temperature as a system of S* = 1/2 Ising spins, weakly interacting ferromagnetically along the 1D polymeric chain (J*/k_B = +0.45 K (+0.5 K) interaction constant estimated for Dy-MOF (Tb-MOF)) and coupled to Ln ions in adjacent chains through dipolar antiferromagnetic interactions. The Dy MOF exhibits slow relaxation of magnetization through a thermally activated process, transitioning to quantum tunneling of the magnetization at low temperatures, while both compounds exhibit field-induced relaxation through a very slow, direct process. The maximum magnetic entropy changes (−ΔS^max_m) for an applied magnetic field change of 2-0 T are 5.71 J kg⁻¹ K⁻¹ and 4.78 J kg⁻¹ K⁻¹, for Dy and Tb MOFs, respectively, while the magnetocaloric effect (MCE) peak for both occurs at T ∼ 1.6 K, approximately double that for the Gd counterpart.