Synthesis of titanium fluorophosphates and fluorosulfates from hexafluorotitanic acid

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Abstract

Three new titanium-based network structures and an organic tetraazapentacenium [TiF6]2– salt were synthesized under high fluoride-concentration, hydrothermal conditions utilizing hexafluorotitanic acid as a starting material. The compositions of the new connected-structure phases obtained are CsTi2F2(PO4)(PO3F)2, [Imidazole-H][Ti3F2(PO3F)(PO4)3]·0.5H2O, and [DABCO-H][Ti(SO4)2(SO3(OH,F))]. CsTi2F2(PO4)(PO3F)2 has a sheet-like structure with interlayer Cs+ ions coordinated solely by fluoride ions, whereas [Imidazole-H] [Ti3F2(PO3F)(PO4)3]·0.5H2O has a three-dimensional framework structure with elliptical channels containing pairs of organic template molecules. The DABCO templated phase is isostructural with ferrinatrite with chains formed from titanium coordinated by six sulfate groups. Reactions using 1,2-phenylenediamine under these conditions surprisingly generates 5,12-dihydro-5,7,12,14-tetraazapentacenium cations, which crystallize as a salt with [TiF6]2–.
Original languageEnglish
Pages (from-to)2766-2770
JournalZeitschrift für Anorganische und Allgemeine Chemie
Volume640
Issue number14
Early online date9 Oct 2014
DOIs
Publication statusPublished - Nov 2014

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fluorophosphate
Titanium
Fluorides
Salts
Ions
Acids
Phase structure
Sulfates
Cations
Molecules
Chemical analysis
imidazole
triethylenediamine

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Synthesis of titanium fluorophosphates and fluorosulfates from hexafluorotitanic acid. / Marshall, Kayleigh A.; Weller, Mark.

In: Zeitschrift für Anorganische und Allgemeine Chemie, Vol. 640, No. 14, 11.2014, p. 2766-2770.

Research output: Contribution to journalArticle

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abstract = "Three new titanium-based network structures and an organic tetraazapentacenium [TiF6]2– salt were synthesized under high fluoride-concentration, hydrothermal conditions utilizing hexafluorotitanic acid as a starting material. The compositions of the new connected-structure phases obtained are CsTi2F2(PO4)(PO3F)2, [Imidazole-H][Ti3F2(PO3F)(PO4)3]·0.5H2O, and [DABCO-H][Ti(SO4)2(SO3(OH,F))]. CsTi2F2(PO4)(PO3F)2 has a sheet-like structure with interlayer Cs+ ions coordinated solely by fluoride ions, whereas [Imidazole-H] [Ti3F2(PO3F)(PO4)3]·0.5H2O has a three-dimensional framework structure with elliptical channels containing pairs of organic template molecules. The DABCO templated phase is isostructural with ferrinatrite with chains formed from titanium coordinated by six sulfate groups. Reactions using 1,2-phenylenediamine under these conditions surprisingly generates 5,12-dihydro-5,7,12,14-tetraazapentacenium cations, which crystallize as a salt with [TiF6]2–.",
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AB - Three new titanium-based network structures and an organic tetraazapentacenium [TiF6]2– salt were synthesized under high fluoride-concentration, hydrothermal conditions utilizing hexafluorotitanic acid as a starting material. The compositions of the new connected-structure phases obtained are CsTi2F2(PO4)(PO3F)2, [Imidazole-H][Ti3F2(PO3F)(PO4)3]·0.5H2O, and [DABCO-H][Ti(SO4)2(SO3(OH,F))]. CsTi2F2(PO4)(PO3F)2 has a sheet-like structure with interlayer Cs+ ions coordinated solely by fluoride ions, whereas [Imidazole-H] [Ti3F2(PO3F)(PO4)3]·0.5H2O has a three-dimensional framework structure with elliptical channels containing pairs of organic template molecules. The DABCO templated phase is isostructural with ferrinatrite with chains formed from titanium coordinated by six sulfate groups. Reactions using 1,2-phenylenediamine under these conditions surprisingly generates 5,12-dihydro-5,7,12,14-tetraazapentacenium cations, which crystallize as a salt with [TiF6]2–.

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