The magnetocaloriceffect is considered as an energy-efficient and environmentally friendly technique which can take cooling technology to the next level. Apart from its commercial application at room temperature, magnetic refrigeration is an up-and-coming solution for the cryogenic regime, especially as an alternative to He³ systems. Molecular magnets reveal advantageous features for ultra-low cooling which are competitive with intermetallic and lanthanide alloys. Here, we present a guide to the current status of magnetocaloric effect research of molecular magnets with a theoretical background focused on the inverse magnetocaloric effect and an overview of recent results and developments, including the rotating magnetocaloric effect.

Octacyanometallate-based compounds displaying a rich pallet of interesting physical and chemical properties, are key materials in the field of molecular magnetism. The [M(CN)₈]ⁿ⁻ complexes, (M = W^V, Mo^V, Nb^IV), are universal building blocks as they lead to various spatial structures, depending on the surrounding ligands and the choice of the metal ion. One of the functionalities of the octacyanometallate-based coordination polymers or clusters is the magnetocaloric effect (MCE), consisting in a change of the material temperature upon the application of a magnetic field. In this review, we focus on different approaches to MCE investigation. We present examples of magnetic entropy change ΔS_m and adiabatic temperature change ΔT_ad, determined using calorimetric measurements supplemented with the algebraic extrapolation of the data down to 0 K. At the field change of 5T, the compound built of high spin clusters Ni₉[W(CN)₈]₆ showed a maximum value of −ΔS_m equal to 18.38 J·K⁻¹ mol⁻¹ at 4.3 K, while the corresponding maximum ΔT_ad = 4.6 K was attained at 2.2 K. These values revealed that this molecular material may be treated as a possible candidate for cryogenic magnetic cooling. Values obtained for ferrimagnetic polymers at temperatures close to their magnetic ordering temperatures, T_c, were lower, i.e., −ΔS_m = 6.83 J·K⁻¹ mol⁻¹ (ΔT_ad = 1.42 K) and −ΔS_m = 4.9 J·K⁻¹ mol⁻¹ (ΔT_ad = 2 K) for {[Mn^II(pyrazole)₄]₂[Nb^IV(CN)₈]·4H₂O}_n and{[Fe^II(pyrazole)₄]₂[Nb^IV(CN)₈]·4H₂O}_n, respectively. MCE results have been obtained also for other -[Nb(CN)₈]-based manganese polymers, showing significant T_c dependence on pressure or the remarkable magnetic sponge behaviour. Using the data obtained for compounds with different T_c, due to dissimilar ligands or other phase of the material, the ΔS_m ~ T_c^−2/3 relation stemming from the molecular field theory was confirmed. The characteristic index n in the ΔS_m ~ ΔHⁿ dependence, and the critical exponents, related to n, were determined, pointing to the 3D Heisenberg model as the most adequate for the description of these particular compounds. At last, results of the rotating magnetocaloric effect (RMCE), which is a new technique efficient in the case of layered magnetic systems, are presented. Data have been obtained and discussed for single crystals of two 2D molecular magnets: ferrimagnetic {Mn^II(R-mpm)₂]₂[Nb^IV(CN)₈]}∙4H₂O (mpm = α-methyl-2-pyridinemethanol) and a strongly anisotropic (tetren)Cu₄[W(CN)₈]₄ bilayered magnet showing the topological Berezinskii-Kosterlitz-Thouless transition.

The magnetocaloric effect (MCE) was investigated in highly anisotropic single crystals of two single molecule magnets (SMMs): [Ln^III(Zn^IIL)₂]CF₃SO₃, where Ln = Tb, Dy and L = tripodal hexadentate Schiff base ligand. The structure of these paramagnetic compounds consists of identically oriented linear trinuclear clusters in a trigonal system with an easy direction c∥Zn–Ln–Zn array and a hard plane ab⊥Zn–Ln–Zn array. The magnitude of MCE measured for c∥H was significantly greater than MCE for ab∥H at a wide temperature range regardless of the studied SMM. Therefore, the rotating magnetocaloric effect (RMCE) was evaluated. The maxima of the magnetic entropy change for RMCE were obtained at 2.0 K and moderate fields: 3.9 J K⁻¹ kg⁻¹ at µ₀H = 1.3 T for Ln = Tb and 3.3 J K⁻¹ kg⁻¹ at µ₀H = 1.1 T for Ln = Dy. The relative efficiency of RMCE compared to the MCE measured in c∥H was as high as 99% at low magnetic fields.