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Magnetic and thermal properties of the iron(III) spin crossover complex [Fe(3MeO-salenEt)(2)]PF(6) are very sensitive to mechanochemical perturbations. Heat capacities for unperturbed and differently perturbed samples were precisely determined by adiabatic calorimetry at temperatures in the 10-300 K range. The unperturbed compound shows a cooperative spin crossover transition at 162.31 K, presenting a hysteresis of 2.8 K. The anomalous enthalpy and entropy contents of the transition were evaluated to be Delta(trs)H = 5.94 kJ mol(-1) and Delta(trs)S = 36.7 J K(-1) mol(-1), respectively. By mechanochemical treatments, (1) the phase transition temperature was lowered by 1.14 K, (2) the enthalpy and entropy gains at the phase transition due to the spin crossover phenomenon were diminished to Delta(trs)H = 4.94 kJ mol(-1) and Delta(trs)S = 31.1 J K(-1) mol(-1), and (3) the lattice heat capacities were larger than those of the unperturbed sample over the whole temperature range. In spite of different mechanical perturbations (grinding with a mortar and pestle and grinding in a ball-mill), two sets of heat capacity measurements provided basically the same results. The mechanochemical perturbation exerts its effect more strongly on the low-spin state than on the high-spin state. It shows a substantial increase of the number of iron(III) ions in the high-spin state below the transition temperature. The heat capacities of the diamagnetic cobalt(III) analogue [Co(3MeO-salenEt)(2)]PF(6) also were measured. The lattice heat capacity of the iron compounds has been estimated from either the measurements on the cobalt complex using a corresponding states law or the effective frequency distribution method. These estimations have been used for the evaluation of the transition anomaly.

A new homologous series of thallium(I) hydrogen dialkanoates, fatty acid thallium soaps, from the dipropane up to the ditetradecane is reported for the first time. This association with 1:1 stoichiometry is the only one exhibited by the thallium derivatives. They have been prepared by solidification of molten mixtures with equimolar proportions of acid and corresponding neutral salt, through crystallization from an anhydrous ethanolic solution of the mixture has also been successful in getting pure compounds with largest chain lengths. Vibrational spectroscopies clearly characterize these crystalline compounds as very strong hydrogen bonding systems. Assignations of active modes in proton and carbon nuclear magnetic resonance spectrometry (NMR) (in ethanol) and infrared (IR) and Raman spectra (in solid state) are reported. According to X-ray diffraction (XRD) they have monomolecular lamellar structures with the acyl chains arranged up and down to the cation/H-bond network in a methyl-to-methyl fashion, and vertically oriented to the basal plane. The acyl chains present all-trans conformation and alternating configuration (perpendicular orthorhombic subcell), like the beta'-phases of other kinds of lipids. Lamellar thickness is reported for the six room-temperature crystalline members. The molecular compounds present polymorphism, one crystal/crystal transition at temperatures close to the peritectical melting. Phase transition thermodynamics are also given and discussed with respect to their acid and salt parents. Their incongruent melting involves nearly 90% of the total enthalpic increments of both constituents' melting processes, making these compounds potential thermal energy storage materials.

Heat capacities of two polyethylene samples, one linear with a density of 0.973 g cm -3 and one branched with a density of 0.91 g cm -3 , have been determined by adiabatic calorimetry from 5 to 360 K in a different experimental arrangement then employed for studies of other polyethylene samples in this series. The heat capacity behavior of these two samples confirms expectations for samples with corresponding densities.