Magnetocaloric effect in M-pyrazole-[Nb(CN)(8)] (M = Ni, Mn) molecular compounds

We report a study of magnetocaloric effect (MCE) in cyanido-bridged {[M(II)(pyrazole)(4)](2)[Nb(IV)(CN)(8)]·4H(2)O}(n) molecular compounds where M = Ni, Mn, pyrazole = C(3)H(4)N(2). The substances show a sharp phase transition to a long range magnetically ordered state, with ferromagnetic coupling between M and Nb sublattices in the case of the Ni-based sample 1 (T(c) = 13.4 K) and ferrimagnetic coupling for the Mn-based sample 2 (T(c) = 23.8 K). The magnetic entropy change ΔS due to applied field change ΔH as a function of temperature was determined by the magnetization and heat capacity measurements. The maximum value of ΔS at μ(0)ΔH = 5 T is 6.1 J mol(-1) K(-1) (5.9 J kg(-1) K(-1)) for 1 at T = 14 K and 6.7 J mol(-1) K(-1) (6.5 J kg(-1) K(-1)) for 2 at T = 25 K. MCE data at different applied fields have been presented as one universal curve, which confirms magnetic transitions in 1 and 2 to be of second order. The temperature dependences of the n exponent characterizing the dependence of ΔS on ΔH have been obtained. The n(T(c)) values, consistent with the shape of the magnetization curves, pointed to the 3D Heisenberg behaviour for 2 and some anisotropy, probably of the XY type, for 1. The (H/T(c))(2/3) dependence of the maximum entropy change has been tested in the ferrimagnetic Mn(2)-L-[Nb(CN)(8)] (L = C(3)H(4)N(2), C(4)H(4)N(2)) series.