True composition and structure of hexagonal "YAlO3", actually Y3Al3O8CO3.

The discovery of a brilliant-blue color upon the introduction of Mn(3+) to the trigonal-bipyramidal (TBP) sites in YInO(3) has led to a search for other hosts for Mn(3+) in TBP coordination. An obvious choice would be YAlO(3). This compound, which has only been prepared through a citrate precursor route, has long been considered isostructural with YInO(3). However, Mn(3+) substitutions into YAlO(3) have failed to produce a product with the anticipated color. We find that the hexagonal structure for YAlO(3) with Al in TBP coordination proposed in 1963 cannot be correct based on its unit cell dimensions and bond-valence sums. Our studies indicate instead that all, or nearly all, of the Al in this compound has a coordination number (CN) of 6. Upon heating in air, this compound transforms to YAlO(3), with the perovskite structure liberating CO(2). The compound long assumed to be a hexagonal form of YAlO(3) is actually an oxycarbonate with the ideal composition Y(3)Al(3)O(8)CO(3). The structure of this compound has been characterized by powder neutron and X-ray diffraction data obtained as a function of temperature, magic-angle-spinning (27)Al NMR, Fourier transform infrared, and transmission electron microscopy. Refinement of neutron diffraction data indicates a composition of Y(3)Al(3)O(8)CO(3). We find that the hexagonal structures of YGaO(3) and YFeO(3) from the citrate route are also stabilized by small amounts of carbonate. Surprisingly, Y(3)Al(3)O(8)CO(3) forms a complete solid solution with YBO(3) having tetrahedral borate groups. Other unlikely solid solutions were prepared in the YAlO(3)-YMnO(3), YAlO(3)-YFeO(3), YAlO(3)-YBO(3), YBO(3)-YMnO(3), YBO(3)-YFeO(3), and YBO(3)-YGaO(3) systems.

[1]  A. Sleight,et al.  Topotactic reduction and reoxidation of hexagonal RCu0.5Ti0.5O3 (R = Y, Eu-Lu) Phases , 2013 .

[2]  J. Gopalakrishnan,et al.  YGa1−xMnxO3: A novel purple inorganic pigment , 2013 .

[3]  F. Morrison,et al.  Structural, magnetic and electrical properties of the hexagonal ferrites MFeO3 (M=Y, Yb, In) , 2012 .

[4]  A. Sleight,et al.  New layered compounds with honeycomb ordering: Li3Ni2BiO6, Li3NiM'BiO6 (M' = Mg, Cu, Zn), and the delafossite Ag3Ni2BiO6. , 2012, Inorganic chemistry.

[5]  A. Sleight,et al.  New oxides showing an intense orange color based on Fe3+ in trigonal-bipyramidal coordination. , 2011, Inorganic chemistry.

[6]  A. Sleight Valency, valence degeneracy, ferroelectricity, and superconductivity , 2009 .

[7]  H. Mizoguchi,et al.  Mn3+ in trigonal bipyramidal coordination: a new blue chromophore. , 2009, Journal of the American Chemical Society.

[8]  R. Seshadri,et al.  Hexagonal YFe1−xPdxO3−δ: Nonperovskite Host Compounds for Pd2+ and Their Catalytic Activity for CO Oxidation , 2008 .

[9]  Jian-fu Li,et al.  White Up-Conversion Luminescence in Rare-Earth-Ion-Doped YAlO3 Nanocrystals , 2008 .

[10]  T. Masui,et al.  Synthesis of crystalline yttrium oxycarbonate in a single phase , 2005 .

[11]  A. Sleight,et al.  Oxygen intercalation of two polymorphs of CuScO2 , 2004 .

[12]  D. Sheptyakov,et al.  Structures and Phase Transition of Vaterite-Type Rare Earth Orthoborates: A Neutron Diffraction Study , 2004 .

[13]  S. Abrahams Ferroelectricity and structure in the YMnO(3) family. , 2001, Acta crystallographica. Section B, Structural science.

[14]  Brian H. Toby,et al.  EXPGUI, a graphical user interface for GSAS , 2001 .

[15]  M. Gervais,et al.  A Multi-nuclear Multiple-Field Nuclear Magnetic Resonance Study of the Y2O3−Al2O3 Phase Diagram , 2001 .

[16]  J. Dahn,et al.  Layered T2-, O6-, O2-, and P2-Type A2/3[M‘2+1/3M4+2/3]O2 Bronzes, A = Li, Na; M‘ = Ni, Mg; M = Mn, Ti , 2000 .

[17]  G. Chadeyron,et al.  Revised Structure of the Orthoborate YBO3 , 1997 .

[18]  V. Caignaert,et al.  Synthesis and Structure of a New Oxycarbonate, Sr5Mn4CO3O10, Closely Related to the Perovskite Structure , 1995 .

[19]  J. Britten,et al.  Synthesis, Crystal Structure, and Unusual Magnetic Properties of InMnO3 , 1995 .

[20]  M. E. Smith Application of27Al NMR techniques to structure determination in solids , 1993 .

[21]  D. Giaquinta,et al.  InMnO 3 : A New Transition Metal Oxide with an Unusual ABO 3 Structure , 1992 .

[22]  P. Slater,et al.  Synthesis and structure of the tetragonal “Ba3YCu2Ox” phase: A perovskite containing carbonate anions , 1991 .

[23]  P. Hagenmuller,et al.  A new variety of LiCoO2 with an unusual oxygen packing obtained by exchange reaction , 1982 .

[24]  R. D. Shannon Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides , 1976 .

[25]  J. Jeffries,et al.  The crystal structure of a new high-temperature modification of YGaO3 , 1975 .

[26]  W. Gebert Die Kristallstruktur von Ba13Al22Si10O66 , 1972 .

[27]  R. Newnham,et al.  Crystal Structure of Yttrium and Other Rare-Earth Borates , 1963 .