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An experimental study of the magnetocaloric effect in tetraaquabis(hydrogen maleato)nickel(II), [Ni(C4H3O4)2(H2O)4] powder sample is presented. The magnetocaloric properties of the studied sample were investigated using specific heat and magnetization measurements in magnetic fields up to 9 T in the temperature range from 0.4 to 50 K. A large conventional magnetocaloric effect was found at a temperature of about 3.5 K, where −ΔSM = 8.5 Jkg−1K−1 and 11.2 Jkg−1K−1 for a magnetic field of 5 T and 7 T, respectively. Assuming a substantial role of the crystal field, the temperature dependence of the magnetic specific heat in a zero magnetic field was compared with an S = 1 model with single-ion anisotropy parameters D and E (axial and rhombic). The best agreement was found for the parameters D/kB = −7.82 K and E/kB = −2.15 K. On the other hand, the experimental temperature dependence of −ΔSM shows higher values compared to the theoretical prediction for the mentioned model, indicating the presence of additional factors in the system, such as an exchange interaction between magnetic ions. The first exchange pathway can be realized through maleic rings between the nearest Ni(II) ions. The second exchange pathway can be realized through water molecules approximately along the a crystallographic axis. Broken-symmetry DFT calculations performed using the computational package ORCA provided the values of ferromagnetic exchange interactions, J1/kB = 1.50 K and J2/kB = 1.44 K (using B3LYP functional). The presence of such ferromagnetic correlations in the studied system may explain the enhanced magnetocaloric effect compared with the model of an anisotropic spin-1 paramagnet. [ABSTRACT FROM AUTHOR]

An experimental study of the rotational magnetocaloric effect in Ni(en)(H2O)4SO4∙2H2O (en = ethylenediamine) single crystal is presented. The study was carried out at temperatures above 2 K and was associated with adiabatic crystal rotation between the easy plane and hard axis in magnetic fields up to 7 T. The magnetocaloric properties of the studied system were investigated by isothermal magnetization measurement. The experimental observations were completed with ab initio calculations of the anisotropy parameters. A large rotational magnetic entropy change ≈12 Jkg−1K−1 and ≈16.9 Jkg−1K−1 was achieved in 5 T and 7 T, respectively. The present study suggests a possible application of this material in low-temperature refrigeration since the adiabatic rotation of the single crystal in 7 T led to a cooldown of the sample from the initial temperature of 4.2 K down to 0.34 K. Finally, theoretical calculations show that S = 1 Ni(II)-based systems with easy-plane anisotropy can have better rotational magnetocaloric properties than costly materials containing rare-earth elements in their chemical structures. [ABSTRACT FROM AUTHOR]

An experimental study is presented of the rotational magnetocaloric effect in a KTm(MoO 4 ) 2 single crystal at temperatures above 2 K associated with the rotation of a single crystal between the magnetic easy and hard axis in constant magnetic fields up to 5 T. The magnetocaloric properties of KTm(MoO 4 ) 2 single crystals are investigated by isothermal magnetization measurements. The maximal rotational entropy change −Δ S R  ≈ 9.8 J/(kgK) is achieved at 10 K in a magnetic field of 5 T. The adiabatic rotation of a single crystal in a field of 5 T at an initial temperature of 4.2 K causes cooling of the sample down to 0.5 K, which indicates an interesting possibility of using this material for cooling processes at low temperatures. [ABSTRACT FROM AUTHOR]

[Ni(fum)(phen)] (fum = fumarato, phen = 1,10 -phenanthroline) has been identified as a system consisting of antiferromagnetic S = 1 dimers with single-ion magnetic anisotropy D comparable to the intradimer exchange coupling J , D / J ≈ 1 and D / k B = −6 K. We present reclassification of the physical model of [Ni(fum)(phen)] magnetic subsystem and the magnetocaloric investigation of a [Ni(fum)(phen)] powder sample at temperatures above 2 K in magnetic fields up to 7 T. The analysis of magnetic specific heat and magnetocaloric effect in [Ni(fum)(phen)] has shown that the temperature dependence of the isothermal entropy change under different magnetic fields is in good agreement with theoretical predictions for the S = 1 ferromagnetic dimer with D / k B = −11.5 K, E / k B = −3.4 K and intradimer exchange coupling J / k B = 2.5 K. Sizeable conventional magnetocaloric effect was found around 5.8 K leading to - ΔS max = 8.2 Jkg−1K−1 for ΔB = 7 T. • Magnetocaloric effect in [Ni(fum)(phen)] – ferromagnetic dimer. • The maximal entropy change –Δ SM ≈ 8.2 J/(Kkg) is achieved in 7 T. • The intradimer ferromagnetic coupling improves the magnetocaloric properties. [ABSTRACT FROM AUTHOR]

Magnetic properties of three variants of MOF-76(Gd), {[Gd(BTC)(H2O)]·G}n (BTC = benzene-1,3,5-tricarboxylate, G = guest molecules) were investigated by static susceptibility, isothermal magnetization and specific heat capacity measurements. In the study we used as synthesized MOF-76(Gd)-DMF (1) (G = DMF = dimethylformamide), containing DMF molecules in the cavity system, compound MOF-76(Gd) (2), activated complex without solvents in the cavities and water exchanged sample MOF-76(Gd)-H2O (3). A pronounced change in the magnetic entropy was found near the critical temperature for all three compounds. It was shown, that magnetic entropy change depends on the solvatation of the MOF. The highest value entropy change, ΔSMpk(T) was observed for compound 2 (ΔSMpk(T) = 42 J kg−1 K−1 at 1.8 K for ΔH = 5 T). The ΔSMpk(T) for the compounds 1, 2 and 3 reached 81.8, 88.4 and 100% of the theoretical values, respectively. This suggests that in compound 3 Gd3+···Gd3+ antiferromagnetic interactions are decoupled gradually, and higher fields promote a larger decoupling between the individual spin centers. The observed entropy changes of compounds were comparable with other magnetic refrigerants proposed for low-temperature applications. To study the magnetothermal effect of 2 (the sample with largest −ΔSMpk), the temperature-dependent heat capacities (C) at different fields were measured. The value of magnetic entropy S obtained from heat capacities (39.5 J kg−1 K−1 at 1.8 K for an applied magnetic field change of 5 T) was in good agreement with that derived from the magnetization data (42 J kg−1 K−1 at 1.8 K). [ABSTRACT FROM AUTHOR]

In our work, we have investigated the magnetocaloric effect (MCE) of core@shell Co@Au nanoparticles by heat capacity C p measurement in temperature range 1.9–55 K under external magnetic field. After the subtraction of lattice heat capacity contribution, the maximum of isothermal magnetic entropy change ΔS m   = 3.11 J K −1 kg −1 was obtained at field change from 0 to 9 T. Adiabatic temperature change ΔT ad   =  3.31 K, refrigerant capacity power RCP = 88.9 J kg −1 and efficiency of adiabatic temperature change η  = 0.37 K/T at the same external magnetic field change were established for the investigated system. The comparison of the results to the independent magnetic measurements data revealed the accordance of fundamental magnetocaloric characteristics obtained by both methods. Thus, this work is also the first experimental confirmation of relation between magnetocaloric response of nanoparticles and the low temperature magnetic transition from superparamagnetic to blocking/freezing state. [ABSTRACT FROM AUTHOR]

The coordination polymer [Gd(PDOA)(NO 3 )(H 2 O) 2 ] n ( 1 ) (PDOA = o -phenylenedioxydiacetato) has been prepared and spectroscopically and structurally characterized. Its crystal structure is formed of a ribbon-like arrangement of Gd(III) atoms linked by bridging carboxylate groups and placed at the cusps of fused triangles with Gd⋯Gd distances of about 6.1 Å. The Gd(III) central atoms exhibit decacoordination by oxygen atoms from hexadentate PDOA ligands with chelating and bridging functions, a chelating nitrato ligand and two aqua ligands. Intra- and intermolecular hydrogen bonds of the O H⋯O and C H⋯O types contribute to the stability of the structure. The temperature dependence of the magnetic susceptibility revealed weak magnetic interactions among Gd(III) ions which may be attributed to dipolar coupling. Investigation of the magnetocaloric effect gives an estimate of the maximum value of isothermal change of magnetic entropy –ΔS m ≈ 35 J kg −1 K −1 which suggests that 1 can be a good material for magnetic cooling at low temperatures. [ABSTRACT FROM AUTHOR]