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Title: F{sup −}/OH{sup −} substitution in [H{sub 4}tren]{sup 4+} and [H{sub 3}tren]{sup 3+} hydroxyfluorotitanates(IV) and classification of tren cation configurations

Abstract

Three [H{sub 3}tren]{sup 3+} or [H{sub 4}tren]{sup 4+} hydroxyfluorotitanates(IV) are solvothermally synthesized from TiO{sub 2}, tren amine, 40% HF aqueous solution and ethanol under microwave heating at 120 °C and 190 °C. [H{sub 4}tren]·(TiF{sub 4.6}(OH){sub 1.4}){sub 2}·2.7H{sub 2}O (I) and β-[H{sub 3}tren]·(TiF{sub 4.5}(OH){sub 1.5})·(F) (II) are described for the first time. The third compound, α-[H{sub 3}tren]·(TiF{sub 4.7}(OH){sub 1.3})·(F) (III), was previously reported as a pure fluorotitanate. The structure determinations are performed from single crystal (I) and powder (II) X-ray diffraction data. The F{sup −}/OH{sup −} substitution, expected from the presence of water in the reaction medium, is characterized by chemical analyses and {sup 19}F MAS solid state NMR experiments: all three structures are built up from Ti(F,OH){sub 6}{sup 2−} octahedra and “free” fluoride ions or water molecules. “Free” fluoride ions are not affected by F{sup −}/OH{sup −} substitution. The electroneutrality is ensured by triprotonated or tetraprotonated tren amines which adopt specific configurations. Additionally, based on the analysis of [H{sub 3}tren]{sup 3+} or [H{sub 4}tren]{sup 4+} hydroxo/oxo/fluorometalates, a classification of the configurations of tren cations is proposed. - Graphical abstract: The ratio of the relative intensities of the {sup 19}F NMR lines assigned to F atoms belonging to isolated TiF{sub 6−x}(OH){submore » x} octahedra and to “free” fluoride ions shows that the F{sup −}/OH{sup −} substitution concerns only F atoms bonded to titanium. - Highlights: • Three tren templated hydroxyfluorotitanates(IV) have been solvothermally synthesized. • They are built up from Ti(F,OH){sub 6}{sup 2−} octahedra and “free” F{sup −} ions or H{sub 2}O molecules. • F{sup −}/OH{sup −} substitution does not affect “free” F{sup −} sites. • [H{sub 4}tren]{sup 4+} and [H{sub 3}tren]{sup 3+} cations adopt specific configurations. • A classification of the configurations of tren cations is proposed.« less

Authors:
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Publication Date:
OSTI Identifier:
22443387
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 217; Other Information: Copyright (c) 2014 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMINES; AQUEOUS SOLUTIONS; CATIONS; CHEMICAL ANALYSIS; ETHANOL; FLUORINE 19; HYBRIDIZATION; MICROWAVE HEATING; MOLECULES; MONOCRYSTALS; NUCLEAR MAGNETIC RESONANCE; POWDERS; SOLIDS; TITANATES; TITANIUM; TITANIUM FLUORIDES; TITANIUM OXIDES; WATER; X-RAY DIFFRACTION

Citation Formats

Lhoste, Jérôme, E-mail: jerome.lhoste@univ-lemans.fr, Body, Monique, E-mail: monique.body@univ-lemans.fr, Legein, Christophe, E-mail: christophe.legein@univ-lemans.fr, Ribaud, Annie, E-mail: annie.ribaud@univ-lemans.fr, Leblanc, Marc, E-mail: marc.leblanc@univ-lemans.fr, and Maisonneuve, Vincent, E-mail: vincent.maisonneuve@univ-lemans.fr. F{sup −}/OH{sup −} substitution in [H{sub 4}tren]{sup 4+} and [H{sub 3}tren]{sup 3+} hydroxyfluorotitanates(IV) and classification of tren cation configurations. United States: N. p., 2014. Web. doi:10.1016/J.JSSC.2014.05.008.
Lhoste, Jérôme, E-mail: jerome.lhoste@univ-lemans.fr, Body, Monique, E-mail: monique.body@univ-lemans.fr, Legein, Christophe, E-mail: christophe.legein@univ-lemans.fr, Ribaud, Annie, E-mail: annie.ribaud@univ-lemans.fr, Leblanc, Marc, E-mail: marc.leblanc@univ-lemans.fr, & Maisonneuve, Vincent, E-mail: vincent.maisonneuve@univ-lemans.fr. F{sup −}/OH{sup −} substitution in [H{sub 4}tren]{sup 4+} and [H{sub 3}tren]{sup 3+} hydroxyfluorotitanates(IV) and classification of tren cation configurations. United States. doi:10.1016/J.JSSC.2014.05.008.
Lhoste, Jérôme, E-mail: jerome.lhoste@univ-lemans.fr, Body, Monique, E-mail: monique.body@univ-lemans.fr, Legein, Christophe, E-mail: christophe.legein@univ-lemans.fr, Ribaud, Annie, E-mail: annie.ribaud@univ-lemans.fr, Leblanc, Marc, E-mail: marc.leblanc@univ-lemans.fr, and Maisonneuve, Vincent, E-mail: vincent.maisonneuve@univ-lemans.fr. Mon . "F{sup −}/OH{sup −} substitution in [H{sub 4}tren]{sup 4+} and [H{sub 3}tren]{sup 3+} hydroxyfluorotitanates(IV) and classification of tren cation configurations". United States. doi:10.1016/J.JSSC.2014.05.008.
@article{osti_22443387,
title = {F{sup −}/OH{sup −} substitution in [H{sub 4}tren]{sup 4+} and [H{sub 3}tren]{sup 3+} hydroxyfluorotitanates(IV) and classification of tren cation configurations},
author = {Lhoste, Jérôme, E-mail: jerome.lhoste@univ-lemans.fr and Body, Monique, E-mail: monique.body@univ-lemans.fr and Legein, Christophe, E-mail: christophe.legein@univ-lemans.fr and Ribaud, Annie, E-mail: annie.ribaud@univ-lemans.fr and Leblanc, Marc, E-mail: marc.leblanc@univ-lemans.fr and Maisonneuve, Vincent, E-mail: vincent.maisonneuve@univ-lemans.fr},
abstractNote = {Three [H{sub 3}tren]{sup 3+} or [H{sub 4}tren]{sup 4+} hydroxyfluorotitanates(IV) are solvothermally synthesized from TiO{sub 2}, tren amine, 40% HF aqueous solution and ethanol under microwave heating at 120 °C and 190 °C. [H{sub 4}tren]·(TiF{sub 4.6}(OH){sub 1.4}){sub 2}·2.7H{sub 2}O (I) and β-[H{sub 3}tren]·(TiF{sub 4.5}(OH){sub 1.5})·(F) (II) are described for the first time. The third compound, α-[H{sub 3}tren]·(TiF{sub 4.7}(OH){sub 1.3})·(F) (III), was previously reported as a pure fluorotitanate. The structure determinations are performed from single crystal (I) and powder (II) X-ray diffraction data. The F{sup −}/OH{sup −} substitution, expected from the presence of water in the reaction medium, is characterized by chemical analyses and {sup 19}F MAS solid state NMR experiments: all three structures are built up from Ti(F,OH){sub 6}{sup 2−} octahedra and “free” fluoride ions or water molecules. “Free” fluoride ions are not affected by F{sup −}/OH{sup −} substitution. The electroneutrality is ensured by triprotonated or tetraprotonated tren amines which adopt specific configurations. Additionally, based on the analysis of [H{sub 3}tren]{sup 3+} or [H{sub 4}tren]{sup 4+} hydroxo/oxo/fluorometalates, a classification of the configurations of tren cations is proposed. - Graphical abstract: The ratio of the relative intensities of the {sup 19}F NMR lines assigned to F atoms belonging to isolated TiF{sub 6−x}(OH){sub x} octahedra and to “free” fluoride ions shows that the F{sup −}/OH{sup −} substitution concerns only F atoms bonded to titanium. - Highlights: • Three tren templated hydroxyfluorotitanates(IV) have been solvothermally synthesized. • They are built up from Ti(F,OH){sub 6}{sup 2−} octahedra and “free” F{sup −} ions or H{sub 2}O molecules. • F{sup −}/OH{sup −} substitution does not affect “free” F{sup −} sites. • [H{sub 4}tren]{sup 4+} and [H{sub 3}tren]{sup 3+} cations adopt specific configurations. • A classification of the configurations of tren cations is proposed.},
doi = {10.1016/J.JSSC.2014.05.008},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 217,
place = {United States},
year = {2014},
month = {9}
}