Syntheses, crystal Structures and electronic Structures of new metal chalcoiodides Bi2CuSe3I and Bi6Cu3S10I

Two new metal chalcoiodides were synthesized by solid-state reactions at 400 degrees C. Crystal Data: Bi2CuSe3I, 1, monoclinic, C2/m, a=14.243(2) angstrom, b=4.1937(7) angstrom, c=14.647(2)angstrom, beta=116.095(2), V=785.7(2) angstrom(3), and Z=4; Bi6Cu3S10I, 2, orthorhombic, Pnma, a=17.476(2) angstrom, b=4.0078(4) angstrom, c=27.391 (2)A, V=1918.5(3) angstrom(3), and Z=4. Compound 1 adopts a three-dimensional structure formed by two alternative layers, which consist of BiSe5 square pyramids, BiSe4I2 octahedra, CuSe4 tetrahedra, and CuSe2I2 tetrahedra. Compound 2 possesses a new open framework built up of BiS5 square pyramides, BiS6 octahedra, BiS8 polyhedra, and CuS4 tetrahedra where I- anions are uniquely trapped within the tunnels. Both electronic structures reveal that bismuth and chalcogenide orbitals dominate the bandgaps. The Cu d and I p states contribute to the top of valence bands, in which the distribution of I orbitals may correspond to the relative bonding interactions in 1 and 2. The optical bandgaps determined by the diffuse reflectance spectra are 0.68 eV and 0.72 eV for 1 and 2, respectively. 1 is a p-type semiconductor with high Seebeck coefficients of 460-575 mu V/K in the temperature range of 300-425 K. The electrical conductivity is 0.02 S/cm at 425 K for the undoped sample. The thermal conductivity is 0.22 W/mK at 425 K. (C) 2015 Elsevier Inc. All rights reserved.