Study Of Double Ionic Disorder (cationic And Anionic) And Disorder Of Two Kinds Of Tin(II) (ionic And Covalent) Within The Same Material: The Incredibly Complex Ba1-xSnxCl1+yF1-y Solid Solution And Its Study By Mössbauer Spectroscopy
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S. Boufas G. Dénès, J. Kochuparampil, H. Merazig & A. Muntasar
AbstractA doubly disordered Ba1-xSnxCl1+yF1-y solid solution has been prepared. X-ray diffraction shows that Ba and Sn are fully disordered on the Ba site of the BaClF structure. In addition, while the two anionic sites remain ordered, for y>0 the y Cl in excess are disordered with the remaining (1-y) F on the F site, whereas for y<0, the (-y) excess F are disordered with the remaining (1+y) Cl on the Cl site. 119Sn Mössbauer spectroscopy showed the Ba1-xSnxCl1+yF1-y solid solution is a truly unique material. Indeed, in addition to the rarity of being a doubly disordered solid solution over a wide range of chemical composition, it also exhibits a variable mixture of ionic tin(II) (Sn2+ stannous ions, with a non-stereoactive lone pair) and covalently bonded tin(II) (with a stereoactive lone pair). A new material, Ba2SnCl6, has been prepared and its crystal structure solved. It contains octahedrally coordinated Sn2+, with a perfectly non-stereoactive lone pair, for the first time in a chloride. This makes the lone pair a potential charge carrier. Keywords: disordered phases, BaClF structure, Mössbauer spectroscopy, X-ray diffraction, mixed conductivity.
disordered phases, BaClF structure, Mössbauer spectroscopy, X-ray diffraction, mixed conductivity.