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Tetrahedrite compounds Cu(12-x)Mn(x)Sb4S13 (0 ≤x≤ 1.8) were prepared by solid state synthesis. A detailed crystal structure analysis of Cu10.6Mn1.4Sb4S13 was performed by single crystal X-ray diffraction (XRD) at 100, 200 and 300 K confirming the noncentrosymmetric structure (space group I4[combining macron]3m) of a tetrahedrite. The large atomic displacement parameter of the Cu2 atoms was described by splitting the 12e site into a partially and randomly occupied 24g site (Cu22) in addition to the regular 12e site (Cu21), suggesting a mix of dynamic and static off-plane Cu2 atom disorder. Rietveld powder XRD pattern and electron probe microanalysis revealed that all the Mn substituted samples showed a single tetrahedrite phase. The electrical resistivity increased with increasing Mn due to substitution of Mn(2+) at the Cu(1+) site. The positive Seebeck coefficient for all samples indicates that the dominant carriers are holes. Even though the thermal conductivity decreased as a function of increasing Mn, the thermoelectric figure of merit ZT decreased, because the decrease of the power factor is stronger than the decrease of the thermal conductivity. The maximum ZT = 0.76 at 623 K is obtained for Cu12Sb4S13. The coefficient of thermal expansion 13.5 ± 0.1 × 10(-6) K(-1) is obtained in the temperature range from 460 K to 670 K for Cu10.2Mn1.8Sb4S13. The Debye temperature, Θ(D) = 244 K for Cu10.2Mn1.8Sb4S13, was estimated from an evaluation of the elastic properties. The effective paramagnetic moment 7.45 μB/f.u. for Cu10.2Mn1.8Sb4S13 is fairly consistent with a high spin 3d(5) ground state of Mn.

The formation, phase relations, crystal chemistry and physical properties were investigated for the solid solution deriving from binary clathrate with a solubility limit of 8 Zn atoms per formula unit at 800 °C ( is a vacancy). Single-crystal x-ray data throughout the homogeneity region confirm the clathrate type I structure with cubic primitive space group type . Temperature-dependent x-ray spectra as well as heat capacity define a low-lying, almost localized, phonon branch, whereas neutron spectroscopy indicates a phonon mode with significant correlations. The transport properties are strongly determined by the Ge/Zn ratio in the framework of the structure. Increasing Zn content drives the system towards a metal-to-insulator transition; for example, shows metallic behaviour at low temperatures, whilst at high temperatures semiconducting features become obvious. A model based on a gap of the electronic density of states slightly above the Fermi energy was able to explain the temperature dependences of the transport properties. The thermal conductivity exhibits a pronounced low-temperature maximum, dominated by the lattice contribution, while at higher temperatures the electronic part gains weight. Zn-rich compositions reveal attractive Seebeck coefficients approaching −180 µV K−1 at 700 K.

Combining experiments and ab initio models we report on SrPt4Ge12 and BaPt4Ge12 as members of a novel class of superconducting skutterudites, where Sr or Ba atoms stabilize a framework entirely formed by Ge atoms. Below T(c)=5.35 and 5.10 K for BaPt4Ge12 and SrPt4Ge12, respectively, electron-phonon coupled superconductivity emerges, ascribed to intrinsic features of the Pt-Ge framework, where Ge-p states dominate the electronic structure at the Fermi energy.

A series of mixed chloro-azole ruthenium complexes with potential antitumor activity, viz., mer-[RuIIICl3(azole)3] (B), trans-[RuIIICl2(azole)4]Cl (C), trans-[RuIICl2(azole)4] (D), and [RuII(azole)6](SO3CF3)2 (E), where azole = 1-butylimidazole (1), imidazole (2), benzimidazole (3), 1-methyl-1,2,4-triazole (4), 4-methylpyrazole (5), 1,2,4-triazole (6), pyrazole (7), and indazole (8), have been prepared as a further development of anticancer drugs with the general formula [RuCl4(azole)2]- (A). These compounds were characterized by elemental analysis, IR spectroscopy, electronic spectra, electrospray mass spectrometry, and X-ray crystallography. The electrochemical behavior has been studied in detail in DMF, DMSO, and aqueous media using cyclic voltammetry, square wave voltammetry, and controlled potential electrolysis. Compounds B and a number of C complexes exhibit one RuIII/RuII reduction, followed, at a sufficiently long time scale, by metal dechlorination on solvolysis. The redox potential values in organic media agree with those predicted by Lever's parametrization method, and the yet unknown EL parameters were estimated for 1 (EL = 0.06 V), 3 (EL = 0.10 V), 4 (EL = 0.17 V), and 5 (EL = 0.18 V). The EL values for the azole ligands 1-8 correlate linearly with their basicity (pK(a) value of the corresponding azolium acid H2L+). In addition, a logarithmic dependence between the homogeneous rate constants for the reductively induced stepwise replacement of chloro ligands by solvent molecules and the RuIII/RuII redox potentials was observed. Lower E(1/2) values (higher net electron donor character of the ligands) result in enhanced kinetic rate constants of solvolysis upon reduction. The effect of the net charge on the RuIII/RuII redox potentials in water is tentatively explained by the application of the Born equation. In addition, the pH-dependent electrochemical behavior of trans-[RuCl2(1,2,4-triazole)4]Cl is discussed.

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The physical properties of single crystals of filled skutterudite compounds EuT 4 Sb 12 (T = Fe, Ru, Os) have been investigated by means of x-ray diffraction, electrical resistivity, specific heat, magnetization, and x-ray absorption spectroscopy measurements. The Eu-based materials crystallize in the LaFe 4 P 12 -type structure (space group I m3 appears to exhibit either canted ferromagnetic or ferrimagnetic order at T C = 88 K whereas EuRu 4 Sb 12 and EuOs 4 Sb 12 are ferromagnets with Curie temperatures of T C = 4 and 9 K, respectively. X-ray absorption near edge spectroscopy measurements reveal a nearly divalent Eu electronic configuration for EuT 4 Sb 12 (T = Fe, Ru, Os) with no significant change with T atom or temperature.