RESUMO
Recrystallization of the solid Cd(10)S(4)(SC(6)H(5))(12) from a solution of pyridine and N, N-di-methylformamide (DMF) results in the formation of the cluster Cd(32)S(14)(SC(6)H(5))(36)-DMF(4) as pale yellow cubes. The structure consists of an 82-atom CdS core that is a roughly spherical piece of the cubic sphalerite lattice approximately 12 angstroms in diameter. The four corners of the lattice are capped by hexagonal wurtzite-like CdS units, which results in an overall tetrahedral cluster approximately 15 angstroms in diameter. This cluster dissolves intact in tetrahydrofuran where its absorption spectrum reveals a sharp peak at 358 nanometers at room temperature and its emission spectra show a strong broad band at 500 nanometers.
RESUMO
The oxygen isotope effect on the superconducting transition temperature (alpha(o)) varies as a function of x in La2-xSrxCuO(4) and La2-xBaxCuO(4), with the maximum alpha(o) values (alpha(o) >/= 0.5) found for x near 0.12. This unusual x dependence implies that the isotope effect is influenced by proximity to the Abma --> P4(2)/ncm structural phase transition in these systems. Synchrotron x-ray difaction measurements reveal little change in lattice parameters or orthorhombicity due to isotope exchange in strontium-doped materials where alpha(o) > 0.5, eliminating static structural distortion as a cause of the large isotope effects. The anomalous behavior of alpha(o) in both strontium- and barium-doped materials, in combination with the previously discovered Abma --> P4(2)/ncm structural phase-transition in La(1.88)B(0.12)CuO(4), suggests that an electronic contribution to the lattice instability is present and maximizes at approximately 1/8 hole per copper atom. These observations indicate a dose connection between hole doping of the Cu-O sheets, tilting instabilities of the CuO(6) octahedra, and superconductivity in La(2)CuO(4)-based superconductors.
