The Korean Journal of Ceramics

The Korean Ceramic Society (한국세라믹학회)
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Tailoring Molecular Precursors for Multicomponent Oxides

  • Hubert-Pfalzgraf, Liliane G. (University de Lyon)
  • Published : 2000.12.01
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Abstract

Simple ways to build up mixed-metal molecules which can act as potential single-source precursors to multimetallic oxides are reviewed. Emphasis is given to Lewis acid-base reactions between metal alkoxides M(OR)/sub n/, and between metal alkoxides and more accessible oxide precursors, carboxylates M(O₂CR)/sub n/ and β-diketonates M(β-dik)/sub n/. Characterization of the precursors is achieved in the solid state (single crystal X-ray diffraction, FT-IR) and by multinuclear NMR in solution. The reactions proceed toward the formation of aggregates in which the different metals display their usual coordinations numbers, often six for transition metals, as shown. Strategies for fixing the stoichiometry between the metals are developed. The reactivity of the MM species (dissociation, effects of chemical modifiers, of other metallic species, hydrolytic or non-hydrolytic condensation, etc.) will be indicated. Transformations into oxides are illustrated on precursors for titanates or niobates.

Keywords

References

  1. Electrooptical Ceramics G.H.Haertling;L.M.Editor(ed.);M.Dekker(ed.)
  2. Processing of Ceramics Metal Alkoxides for Electrooptical Ceramics L.G.Hubert-Pfalzgraf
  3. Appl. Organo-metal. Chem. v.6 Metal Alkoxides and ?-Diketonates as Precursors for Oxide and Non-oxide Thin Films L.G.Hubert-Pfalzgraf
  4. New J. Chem v.11 Alkoxides as Molecular Precursor for Oxide Based Materials:Opportunities for New Materials L.G.Hubert-Pfalzgraf
  5. Metal Alkoxides D.C.Bradley;R.C.Mehrotra;D.P.Gaur
  6. Chem. Rev. v.93 Chemical Aspects of Solution Routes to Perovskite-Phase Mixed-Metal Oxides From Metal0\-Organic Precursors D.C.Chandler;C.Roger;M.J.Hampden-Smith
  7. Chem. Rev. v.90 Synthesis, Structural Principles and Reactivity of Heterometallic Alkoxides K.G.Caulton;L.G.Hubert-Pfalzgraf
  8. Polyhecron v.13 Mixed-Metal Alkoxides and Oxoal-koxides a s Intermediates on Chemical Routes to Materials L.G.Hubert-Pfalzgraf
  9. Polyhedron v.15 Synthesis and Characterization of Volatile Mixed-Metal Yttrium-Barium, Barium-Copper and Yittrium-copper ?-Diketonatofluoroisopropoxides. Molecular Structure of Ba-Y₂(thd)₄[OCH(CF₃)₂]₄ F.Labrize;L.G.Hubert-Pfalzgraf;J.C.Daran;P.Tobaly
  10. Chem Mater v.8 Synthesis of Lithium Niobate Gels Using a Metal Alkoxide-Metal Nitrate Precursor H.C.Zeng;S.K.Tung
  11. J. Chem. Soc. Chem. Commun Lead(Ⅱ) Oxoallkoxides as Complex Ligands:Syn-Thesis and Molecular Structure of Pb?O₄(OEt)₄[Nb(OEt)?]₄ R. Papiernik,;L.G.Hubert-Pfalzgraf;J.C.Daran;Y.Jeannin
  12. Inorg. Chem. v.34 Single-Source Precursors of Lead Titanater Synthesis, Molecular Structure and Reactivity of PbTiO(OPr) S.Daniele;R.Papiernik;L.G.Hubert-Pfalzgraf;S.Jagner;M.Hakansson
  13. J. Mater. Chem. v.7 Slution Routes to Lead Titanate L.G.Hubert-Pfalzgraf;S.Daniele;R.Papiernik;M.C.Massiani;J.Vaissermann
  14. New J. Chem v.19 Toward Molecular Design of Lanthanides Homo and Heterometallic Precursors of Oxide Based Materials L.G.Hubert-Pfalzgraf
  15. Polyhedron v.13 Synthesis and Molecular Structure of Sm₄TiO(OPr?)?, a Novel Framework for Heterometallic Alkoxides with a 1:4 Stoichiometry S.Daniele;L.G.Hubert-Pfalzgraf;J.C.Daran;S.Halut
  16. Science v.246 J.F.Scott;C.A.Paiz de Araujo
  17. Chem.Mater. v.8 K.R.Kendall;C.Navas;J.K.Thomas;H.C.zurLoye
  18. Chem. Mater. v.10 Sol-Gel preparation of Bi₂M?V?O? delta (M=Cu,Nb,x=0.1,0.3) J.W.Pell;K.M.Delak;H.C.Zur Loye
  19. Better Ceramics Through Chemistry VI v.346 Mixed-metal Bismuth-Titanium Species. Chemical Routes to Bi₄Ti₃O? R.Papiernik;L.G.Hubert-Pfalzgraf;S.Parola;S.Jagner;F.Soares-Carvalho;P.Thomas;J.P.Mercurio
  20. J.Chem. Soc. Dalton Trans. v.23 Activation of Bismuth Alkoxides:Synthesis Molecular Structure and Reactivity of the Bi₂(?₃-O)(?-OR)₄(OR)? and [Bi₂(OR)₄(acac)₂](R=Pr?) R.Papiernik;L.G.Hubert-Pfalzgraf;S.Parola;S.Jagner;F.Soares-Carvalho;P.Thomas;J.P.Mercurio
  21. J. Sol-gel Science Technol v.2 S.Boulnnaaz;L.G.Hubert-Pfalzgraf
  22. J. Chem. Soc. Shem. Commun Synthesis and Characterization of Tantalum-Zinc Oxoisopropoxides: Molecular Structure of [ZnTa₂(?₄-O)(?-O)(?-OPr?)₃(OPr?)₄]₂ S.Boulnnaaz;L.G.Hubert-Pfalzgraf
  23. Polyhedron v.17 Chemical Routes to Barium-Cerium Oxides. Molecular Structure of Ba₄Ce₂(??-O)(thd)₄(?₃-OPr?)?(OPr?)2 L.G.Hubert-Pfalzgraf;C.Sirio;C.Bois
  24. J. Coord. Chem. Rev. v.178-180 Some Aspects of Functional Homo and Heterometallic Alkoxides L.G.Hubert-Pfalzgraf
  25. J. Solid State Chem v.98 Hydrolysis of Mixed Titanium and Zirconium Alcoxides by an Sterification REaction L.Laaziz;A.Larbot;A.Julbe;C.Guizard;L.Cot
  26. J. Non Cryst. Sol. Structure of Zr2Ti2O4(OiPr)8(OPr)2(OAc)6 I.Laaziz;A.Larbot;J.D.Foulon;L.Cot
  27. Russ.J.Inorg. Chem. v.40 Synthesis and sTructure of BaTi and Ca-Ti Metallic Alcoholates A.I.Yanovskii;E.P.Turevskoya;M.I.Yarouskoya;V.G.Kessler;N.YaTurova
  28. Chem. Mater. v.6 Single-source Precursors for BaTiO3:Synthesis, Characterization of β-diketomatoalkoxide and Molecular Structure of Ba2Ti2(thd)4(OEt)8(EtOH)2 V.G.Kessler;S.Daniele;L.G.Hubert-Pfalzgraf;A.Gleizes
  29. J. Sol-gel Science Tech. v.8 Molecular Disign of Single Source BaTiO3 and SrTiO3 Precursors L.G.Hubert-Pfalzgraf;S.Daniele;J.M.Dacams
  30. Metal β-dinketonates and Allied Derivatives R.C.Mehrotra;R.Bohra;D.P.Gaur
  31. Better ceramics Through Chemistry VI v.346 Controlling the Properties of Bulk Metal Oxides at a Molecular Level:Alkoxides vs Carboxylates Alkoxides Routes L.G.Hubert-Pfalzgraf;S.Daniele;S.Boulmaaz;R.Papiernik
  32. Pb. J. Mater. Chem. v.7 Molecular Constithesis, Molecular Structure and Reactivity of MNb2(?-OAc)2(OPri)10 M=Mg,Cd S.Boulmaaz;R.Papiernik;L.G.Hubert-Pfalzgraf;J.C.Daran
  33. Inorg. Chem. v.34 Influence of Lead(Ⅱ) Lone Pairs on the Serpentine Structure for Heter Ometallic Alkoxides D.J.Teff;J.C.Huffman;K.G.Caulton
  34. Inorg. Chem. v.36 Heterometallic Alkoxides of Zironium with Tin(Ⅱ) or Lead(Ⅱ) D.J.Teff;J.C.Huffman;K.G.Caulton
  35. J. Sol-Gel Science Techn v.8 Ester Elimination : a General Solvent Dependent Non-Hydrolytic Routes to Metal and Mixed-Metal Oxides J. Caruso;M.J.Hampden-Smith
  36. Comments Inorg. Chem. v.16 An Investigation of Group IV Alkoxides as Property Control Reagents in the Synthesis of Ceramics Materials T.J.Boyle;R.W.Schwartz
  37. Inorg. Chem. v.29 Alcohols Adducts of Alkoxides:Intramolecular Bydrogen Bonding as a General Structural Feature B.A.;Vaartstra;J.C.Huffman;P.S.Gradeff;L.G.Hubert-Pfalzgraf;J.C.Daran;S.Parraud;K.Yunlu;K.G.Caulton
  38. J. Chem. Soc. Chem. Commun v.705 REactions of Coordinated Ligands Topological and Stoichiometric Control for Mixed-Metal Alkoxides V.G.Kessler;L.G.Hubert-Pfalzgraf;S.Halut;J.C.Daran
  39. Polyhedron Formation of Mixed-Metal Alkoxides Mediated by the Reactivity of Coordinated Pinacol. Molecular Structure of Ce-Ti and Ce-Nb Species V.Abada;L.G.;Hubert-Pfalzgraf;J.Vaissermann
  40. Better Ceramics Through Chemistry v.346 29Si,17O Liquid NMR and 29Si CP-MAS NMR Characterization of Siloxane-Oxide Materials (Me2-SiO/TiO2, MeSiOZrO2 ) F. Babonneau
  41. Better Ceramics Through ChemistryⅡ v.73 Chemical Routes to Aluminosilicate Gels, Glasses and Ceramics J.C.Plouxviel;J.P.Bailot;A.Dauger;J.C.Boilot;L.G.Hubert-Pfalzgraf
  42. Jpn J.Appl. Phys. v.32 Synthesis and Characterization of Bi4Ti3O12 Thin Films by Sol-Gel Processing M.Toyoda;Y.Tamaji;K.Tomono;D.A.Payne
  43. Better Ceramics through Chemistry VII v.435 Molecules with Polymerizable Ligands as Precursors to Organic Porous Solids N.Pajot;R.papiernik;L.G.Hubert-Pfalzgraf;S.Paraud
  44. J. Mater. Res. v.7 Preparation of Pb(Zr1-x-Tiz)O3 Powders from Complex Alkoxide and Their Lower Temperature Crystallisation T.Fukui;C.Sakurai;M.Okuyama
  45. J. Chen. Soc. Dalton Trans. Synthesis and Molecular Structure of Bi4Ba4(?4-O)2(?3-OEt)8(?-OEt)4(?2-thd)4 an Example of the Formation of a Mixed-Metal Alkoxide Assisted by Dioxygen S.Parola;R.Papiernik;L.G.Hubert-Pfalzgraf;J.Vaissermann