Sr sub(3)Bi sub(2)(SeO sub(3)) sub(6).H sub(2 )O: A novel anionic layer consisting of second-order Jahn-Teller (SOJT) distortive cations

• Published in: Journal of solid state chemistry Vol. 221; pp. 73 - 78
• Main Authors: Ahn, Hyun Sun, Lee, Eun Pyo, Chang, Hong-Young, Lee, Dong Woo, Ok, Kang Min
• Format: Journal Article
• Language: English
• Published: 01.01.2015
• Subjects: Bismuth; Cations; Diffraction; Distortion; Electronic structure; Hydrates; Mathematical analysis; Polyhedrons; Reflectance
• ISSN: 0022-4596
• DOI: 10.1016/j.jssc.2014.09.018

A new layered bismuth selenite hydrate material, Sr sub(3)Bi sub(2)(SeO sub(3)) sub(6).H sub(2)O has been synthesized through a hydrothermal reaction using SrCO sub(3), Bi sub(2)O sub(3), SeO sub(2), and water as reagents. The crystal structure of the reported material has been determined by single crystal X-ray diffraction analysis. The anionic layered framework of Sr sub(3)Bi sub(2)(SeO sub(3)) sub(6).H sub(2)O consists of polyhedra of second-order Jahn-Teller (SOJT) distortive cations, Bi super(3+) and Se super(4+). Attributable to the variable and asymmetric coordination geometry of the constituent cations, a rich structural chemistry including uni-dimensional bands and linkers is observed in the layer. The material is thermally stable up to about 390 degree C and starts decomposing due to the sublimation of SeO sub(2) above the temperature. The UV-vis diffuse reflectance spectrum suggests a band gap of 3.3 eV. Elemental analysis, infrared spectrum, local dipole moment calculations, and electronic structure calculations are also reported. Ball-and-stick and polyhedral representation of Sr sub(3)Bi sub(2)(SeO sub(3)) sub(6).H sub(2)O in the ab-plane. The stereoactive lone pairs are visualized around the Bi super(3+) and Se super(4+) as lobelike isosurfaces through ELF calculations with eta =0.9.