RESUMEN
Samples with the nominal composition Cu0.9Pb1.2Sb2.9Se6 mainly contain a phase with incommensurately modulated lillianite-type structure with the respective composition. Single crystal diffraction with synchrotron radiation enabled a detailed refinement using the superspace group Cmcm(α00)00s with lattice parameters a = 4.16537(5), b = 14.0821(2), c = 19.8234(3) Å, and a modulation vector q = 0.6890(2)a* at room temperature. The structure is built up from tilted and distorted NaCl-type slabs that are interconnected by bicapped trigonal prisms, which mainly host Pb atoms, according to a 4L arrangement. Satellites up to the second order reveal positional and occupational modulation that mainly involves a sequence of Sb and Cu atoms and allows the Se substructure to adapt in a way that Sb and Cu feature predominantly octahedral and tetrahedral coordination, respectively. Above 523 K, satellite reflections disappear, and the crystal structure becomes more disordered with average coordination spheres of both Sb and Cu atoms corresponding to distorted octahedra. This phase transition leads to discontinuities in the evolution of lattice parameters and physical properties as functions of temperature. HRTEM investigations corroborate centrosymmetry and highlight atoms that are strongly affected by the modulation. Measurements of transport properties reveal a p-type semiconductor with a thermoelectric figure of merit up to 0.1 at 623 K. In accordance with B factor analysis, a small amount of substitution could increase zT significantly by optimizing the carrier concentration.
RESUMEN
The controlled adsorption of polynuclear coordination compounds with specific structural and electronic characteristics on surfaces is crucial for the prospective implementation of molecule-surface interfaces into practical electronic devices. From this perspective, a neutral 3d,4f-coordination cluster [MnII3MnIVYb3O3(OH)(L·SMe)3(OOCMe)9]·2MeCN·3EtOH (1·2MeCN·3EtOH), where L·SMe- is a Schiff base, has been synthesized and fully characterized and its adsorption on two different solid substrates, gold and graphite, has been studied. The mixed-valence compound with a bilayered metal core structure and the structurally exposed thioether groups exhibits a substantially different surface bonding to metallic gold and semimetallic graphite substrates. While on graphite the adsorption takes place only on distinguished attraction points with a locally increased number of potential bonding sites such as terrace edges and other surface defects, on gold the molecules were found to adsorb rather weakly on randomly distributed adsorption sites of the surface terraces. This entirely different behavior provides important information for the development of advanced surface materials that may enable well-distributed ordered molecular assemblies.