Cage compound Sc5Pt24B12: a Pt-stuffed variant of filled skutterudite structure. Electronic and structural properties.

Abstract

The title compound was obtained from elements via arc melting and its crystal structure was determined from single-crystal X-ray diffraction data (space group Im3̄, a = 10.2042(6) Å). The refinement indicated the occupancy of icosahedral 2a and cubooctahedral 8c sites solely by Sc atoms which leads to the composition Sc5Pt24B12 in contrast to the previously reported ternary stannides of Gd3Ni8Sn16 type (RE5-xM12Sn24(+x) compounds). The compound is the first representative of borides crystallizing with a site exchange variant of this stannide structure type. The structural relationships of the boride structure and filled skutterudite LaFe4P12vs. the Remeika phase of Yb3Rh4Sn13-type are discussed. Analysis of chemical bonding classifies Sc5Pt24B12 as a cage compound exhibiting the ionic interaction of cationic scandium species in the cages of anionic framework, formed by covalently bonded B and Pt atoms. Electronic structure calculations show that the electronic states of atoms centered around the cubooctahedral 8c site, i.e. Sc2 3d-, Pt2 5d- and B 2p-states dominate the density of states (DOS) at the Fermi level EF. Strong effect of spin-orbit coupling on the band structure at the gamma point has been found from density functional theory calculations. Sc5Pt24B12 exhibits superconductivity with a transition temperature of TC = 2.45 K.