title: Investigation of new alkali bismuth oxosulfates and oxophosphates with original topologies of oxo-centered units.
abstract: Two new alkali bismuth oxosulfates, [Bi12O15]Li2(SO4)4 (I) and [Bi7K2O8]K(SO4)4 (II), have been synthesized by heating a mixture of Bi2O3, CuSO45H2O, and A2CO3 (A = Li, K), and characterized by single crystal XRD, transmission electron microscopy, and multiphoton SHG and IR spectroscopy. In the above formula the [BixOy] subunits denote the 3D-porous (I) or 1D-columnar (II) polycationic host-lattice formed of edge-sharing OBi4 or O(Bi,K)4 oxocenterd tetrahedra. The SO4(2-) groups and alkali ions are arranged into channels in the interstices leading to original opened crystal structures for these two first reported alkali oxo-bismuth sulfates. The strong adaptability of the oxocentered framework is demonstrated by the possibility of preparing single crystals of [Bi8.73K0.27O8]K1.54(PO4)4 (III) whose crystal structure is similar to those of II with disorder between OBi4 and O(Bi3,K) tetrahedra and different channel occupancy due to the aliovalent replacement of SO4(2-) for PO4(3-).
authors.affiliation: Université Lille Nord de France, UMR 8181 CNRS, Unité de Catalyse et de Chimie du Solide (UCCS USTL) , F-59655 Villeneuve d'Ascq, France.
authors.forename: Minfeng
authors.initials: M
authors.lastname: Lü
authors.forename: Marie
authors.initials: M
authors.lastname: Colmont
authors.forename: Marielle
authors.initials: M
authors.lastname: Huvé
authors.forename: Isabelle
authors.initials: I
authors.lastname: De Waele
authors.forename: Christine
authors.initials: C
authors.lastname: Terryn
authors.forename: Almaz
authors.initials: A
authors.lastname: Aliev
authors.forename: Olivier
authors.initials: O
authors.lastname: Mentré
mesh_terms: D001729:Bismuth / Q000737:chemistry*; D004553:Electric Conductivity; D008672:Metals, Alkali / Q000737:chemistry*; D018613:Microscopy, Confocal; D046529:Microscopy, Electron, Transmission; D010087:Oxides / Q000737:chemistry*; D010710:Phosphates / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared; D013431:Sulfates / Q000737:chemistry*; D014961:X-Ray Diffraction
chemical_list: D008672:Metals, Alkali; D010087:Oxides; D010710:Phosphates; D013431:Sulfates; D001729:Bismuth