Specific chemistry of the anions: [TaOF5]2-, [TaF6]-, and [TaF7]2-

Hongcheng Lu; Romain Gautier; Martin D. Donakowski; Lindsay Fuoco; Zhengtang Liu; Kenneth R. Poeppelmeier

doi:10.1021/cg401710j

Specific chemistry of the anions: [TaOF₅]^2-, [TaF₆]^-, and [TaF₇]^2-

Hongcheng Lu, Romain Gautier, Martin D. Donakowski, Lindsay Fuoco, Zhengtang Liu, Kenneth R. Poeppelmeier

Northwestern University

Research output: Contribution to journal › Article › peer-review

12 Citations (Scopus)

Abstract

The controlled crystallization of specific tantalum oxide-fluoride and tantalum fluoride anions ([TaOF₅]^2-, [TaF ₆]^-, and [TaF₇]^2-) is demonstrated using organic reagents with varied corresponding pK_a values in the presence of aqueous hydrofluoric acid. The identity of tantalum oxide-fluoride or fluoride anions of [TaOF₅]^2-, [TaF₆] ^-, and [TaF₇]^2- are shown to crystallize successively from solution to solid state by increasing the corresponding pK_a of organic reagents, which lead to the subsequent increase of fluoride concentration in the hydrofluoric acid solution. With the use of this methodology, three new hybrid crystal structures were targeted: [H ₂(2,2′-bpy)]TaOF₅ (2,2′-bpy = 2,2′-bipyridyl) 1, [Hdpa]TaF₆ (dpa = 2,2′-dipyridylamine) 2, and [H₂En]TaF₇ (En = ethylenediamine) 3, respectively. The applicability and comparison of this methodology for tantalum and previously prepared niobium compounds show that it can be broadly used to design new materials with specific functionalities for other transition metal oxide-fluorides.

Original language	English
Pages (from-to)	844-850
Number of pages	7
Journal	Crystal Growth and Design
Volume	14
Issue number	2
DOIs	https://doi.org/10.1021/cg401710j
Publication status	Published - Feb 5 2014

ASJC Scopus subject areas

Chemistry(all)
Materials Science(all)
Condensed Matter Physics

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title = "Specific chemistry of the anions: [TaOF5]2-, [TaF6]-, and [TaF7]2-",

abstract = "The controlled crystallization of specific tantalum oxide-fluoride and tantalum fluoride anions ([TaOF5]2-, [TaF 6]-, and [TaF7]2-) is demonstrated using organic reagents with varied corresponding pKa values in the presence of aqueous hydrofluoric acid. The identity of tantalum oxide-fluoride or fluoride anions of [TaOF5]2-, [TaF6] -, and [TaF7]2- are shown to crystallize successively from solution to solid state by increasing the corresponding pKa of organic reagents, which lead to the subsequent increase of fluoride concentration in the hydrofluoric acid solution. With the use of this methodology, three new hybrid crystal structures were targeted: [H 2(2,2′-bpy)]TaOF5 (2,2′-bpy = 2,2′-bipyridyl) 1, [Hdpa]TaF6 (dpa = 2,2′-dipyridylamine) 2, and [H2En]TaF7 (En = ethylenediamine) 3, respectively. The applicability and comparison of this methodology for tantalum and previously prepared niobium compounds show that it can be broadly used to design new materials with specific functionalities for other transition metal oxide-fluorides.",

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AU - Lu, Hongcheng

AU - Gautier, Romain

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AU - Fuoco, Lindsay

AU - Liu, Zhengtang

AU - Poeppelmeier, Kenneth R.

PY - 2014/2/5

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N2 - The controlled crystallization of specific tantalum oxide-fluoride and tantalum fluoride anions ([TaOF5]2-, [TaF 6]-, and [TaF7]2-) is demonstrated using organic reagents with varied corresponding pKa values in the presence of aqueous hydrofluoric acid. The identity of tantalum oxide-fluoride or fluoride anions of [TaOF5]2-, [TaF6] -, and [TaF7]2- are shown to crystallize successively from solution to solid state by increasing the corresponding pKa of organic reagents, which lead to the subsequent increase of fluoride concentration in the hydrofluoric acid solution. With the use of this methodology, three new hybrid crystal structures were targeted: [H 2(2,2′-bpy)]TaOF5 (2,2′-bpy = 2,2′-bipyridyl) 1, [Hdpa]TaF6 (dpa = 2,2′-dipyridylamine) 2, and [H2En]TaF7 (En = ethylenediamine) 3, respectively. The applicability and comparison of this methodology for tantalum and previously prepared niobium compounds show that it can be broadly used to design new materials with specific functionalities for other transition metal oxide-fluorides.

AB - The controlled crystallization of specific tantalum oxide-fluoride and tantalum fluoride anions ([TaOF5]2-, [TaF 6]-, and [TaF7]2-) is demonstrated using organic reagents with varied corresponding pKa values in the presence of aqueous hydrofluoric acid. The identity of tantalum oxide-fluoride or fluoride anions of [TaOF5]2-, [TaF6] -, and [TaF7]2- are shown to crystallize successively from solution to solid state by increasing the corresponding pKa of organic reagents, which lead to the subsequent increase of fluoride concentration in the hydrofluoric acid solution. With the use of this methodology, three new hybrid crystal structures were targeted: [H 2(2,2′-bpy)]TaOF5 (2,2′-bpy = 2,2′-bipyridyl) 1, [Hdpa]TaF6 (dpa = 2,2′-dipyridylamine) 2, and [H2En]TaF7 (En = ethylenediamine) 3, respectively. The applicability and comparison of this methodology for tantalum and previously prepared niobium compounds show that it can be broadly used to design new materials with specific functionalities for other transition metal oxide-fluorides.

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