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  • Author or Editor: M. Sorai x
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Abstract  

The heat capacities and magnetic susceptibilities of powdered samples of FexNbS2 (x=0.14, 0.21 and 0.30) were measured at temperatures from 8 to 303 K and from 5 to 300 K, respectively. For Fe0.14NbS2, the magnetic susceptibility exhibited an anomaly as a shoulder at about 57 K, but no heat capacity anomaly was observed at this temperature, indicating the appearance of a spin-glass state. Anomalies in the heat capacity for FexNbS2 (x=0.21 and 0.30) occurred at 100.5 and 45.0 K, respectively, where the magnetic susceptibility displayed a maximum, corresponding to an antiferro-paramagnetic phase transition. The electronic state of the iron atom is discussed on the basis of entropy analysis.

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Summary Heat capacity measurements of the two-dimensional metal-assembled complex, (NEt4)[{MnIII(salen)}2FeIII(CN)6] [Et=ethyl, salen= N,N’-ethylenebis(salicylideneaminato) dianion], were performed in the temperature range between 0.2 and 300 K by adiabatic calorimetry. A ferrimagnetic phase transition was observed at T c1=7.51 K. Furthermore, another small magnetic phase transition appeared at T c2=0.78 K. Above T c1, a heat capacity tail arising from the short-range ordering of the spins characteristic of two-dimensional magnets was found. The magnetic enthalpy and entropy were evaluated to be ΔH=291 J mol-1 and ΔS=27.4 J K-1 mol-1, respectively. The experimental magnetic entropy agrees roughly with ΔS=Rln(5·5·2) (=32.5 J K-1 mol-1; R being the gas constant), which is expected for the metal complex with two Mn(III) ions in high-spin state (spin quantum number S=2) and one Fe(III) ion in low-spin state (S=1/2). The heat capacity tail above T c1 became small by grinding and pressing the crystal. This mechanochemical effect would be attributed to the increase of lattice defects and imperfections in the crystal lattice, leading not only to formation of the crystal with a different magnetic phase transition temperature but also to decrease of the magnetic heat capacity and thus the magnetic enthalpy and entropy.

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