Titre du document / Document title

Synthesis, structures, and reactivity of two compounds containing the tancoite-like [Ga(HPO₄)₂F]^2-∞ chain

Auteur(s) / Author(s)

WALTON R. I. ⁽¹⁾ ; MILLANGE F. ⁽¹⁾ ; O'HARE D. ⁽¹⁾ ; PAULET C. ⁽²⁾ ; LOISEAU T. ⁽²⁾ ; FEREY G. ⁽²⁾ ;

Affiliation(s) du ou des auteurs / Author(s) Affiliation(s)

⁽¹⁾ Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QR, ROYAUME-UNI
⁽²⁾ Institut Lavoisier, UMR CNRS 8637, Université de Versailles St Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles, FRANCE

Résumé / Abstract

Compounds containing the one-dimensional macroanion [Ga(HPO₄)₂F]^2- have been synthesized using ambient and moderate solvothermal conditions, and their interconversion and reactivity studied. The anionic chains exist in the hydrated gallium fluorophosphate (1) Ga(HPO₄)₂F.(NH₃(CH₂)₃NH₃).2H₂O, synthesized at room temperature from an aqueous reaction. Heating 1 in air at 70°C gives the dehydrated form 2 or Ga(HPO₄)₂F.(NH₃(CH₂)₃NH₃). 2 can also be solvothermally prepared at 120 °C from a water/DMF mixture and has been characterized by single-crystal X-ray diffraction. It is orthorhombic (space group Pbcm (no. 57), a = 8.642(2) Å, b = 19.346(13) Å, c = 7.114(4) Å, V = 1189.3(11) ų), and refined to R1(F) = 0.0384 and wR2(F²) = 0.0704 for reflections with I > 2σ(I). Both the structures contain anionic chains of corner-sharing GaO₄F₂ octahedra linked together via fluorine and PO₄ tetrahedra, the topology of which is the same as in the aluminophosphate mineral tancoite. Both 1 and 2 when heated with water under hydrothermal conditions produce the open-framework, three-dimensional phase ULM-3 without addition of any other reagents. This process has been followed in situ with time-resolved energy-dispersive diffraction, which reveals that dissolution of the one-dimensional phase occurs before the rapid crystallization of ULM-3.

Revue / Journal Title

Chemistry of materials   ISSN 0897-4756 

Source / Source

2000, vol. 12, n^o 7 (266 p.)  (41 ref.), pp. 1977-1984

Langue / Language

Anglais

Editeur / Publisher

American Chemical Society, Washington, DC, ETATS-UNIS  (1989) (Revue)

Mots-clés anglais / English Keywords

Experimental study ; Chemical preparation ; Gallium complex ; Fluoro complex ; Anionic complex ; Organic dication ; Ammonium Organic compounds ; Hydrates ; Heat treatment ; Dehydration ; Chemical reactivity ; Hydrothermal synthesis ; Porous material ; Microporosity ; Crystallization ; Topology ; Solvothermal synthesis ; Hybrid material ; Open framework ;

Mots-clés français / French Keywords

Etude expérimentale ; Préparation chimique ; Gallium complexe ; Complexe fluoro ; Complexe anionique ; Dication organique ; Ammonium Composé organique ; Hydrate ; Traitement thermique ; Déshydratation ; Réactivité chimique ; Synthèse hydrothermale ; Matériau poreux ; Microporosité ; Cristallisation ; Topologie ; Complexe hydrogénophosphato ; ULM3 ; Synthèse solvothermale ; Matériau hybride ; Structure ouverte ;

Mots-clés espagnols / Spanish Keywords

Estudio experimental ; Galio complejo ; Complejo fluoro ; Complejo aniónico ; Dicatión orgánico ; Amonio Compuesto orgánico ; Hidrato ; Tratamiento térmico ; Deshidratación ; Reactividad química ; Material poroso ; Microporosidad ; Cristalización ; Topología ;

Localisation / Location

INIST-CNRS, Cote INIST : 21957, 35400009082182.0280