From solution to the solid state: Control of niobium oxide-fluoride [NbOxFy]n- species

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

doi:10.1021/ic402561g

From solution to the solid state: Control of niobium oxide-fluoride [NbO_xF_y]^n- species

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

Northwestern University

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

11 Citations (Scopus)

Abstract

In this study, we describe the crystallization of specific niobium oxide-fluoride anions (either [NbOF₄]^- or [NbOF ₅]^2-) by increasing the fluoride concentration with the appropriate use of organic bases with varied corresponding pK_a values to create suitable equilibria for the formation of each anion. HpyNbOF ₄ (I; py = pyridine) contains the [NbOF₄]^- anion, while [H₂(4,4′-bpy)]NbOF₅] (II; 4,4′-bpy = 4,4′-bipyridyl) contains the [NbOF₅] ^2- anion; their identity is correlated with reagent ratios. The increase of basic species (proton acceptors) results in an increase in the fluoride concentration and high fluoride-containing anions. The crystallization of [NbOF₄]^- in [NbO_2/2F₄] _∞ chains in I was controlled with the use of weak base pyridine (pK_a = 5.23), while isolated [NbOF₅]^2- crystallized in II with strong base 4,4′-bipyridyl (pK_a = 10.5). This approach can be broadly applied to target-specific basic building units for fundamentally new and potentially functional solid-state materials.

Original language	English
Pages (from-to)	537-542
Number of pages	6
Journal	Inorganic Chemistry
Volume	53
Issue number	1
DOIs	https://doi.org/10.1021/ic402561g
Publication status	Published - Jan 6 2014

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "From solution to the solid state: Control of niobium oxide-fluoride [NbOxFy]n- species",

abstract = "In this study, we describe the crystallization of specific niobium oxide-fluoride anions (either [NbOF4]- or [NbOF 5]2-) by increasing the fluoride concentration with the appropriate use of organic bases with varied corresponding pKa values to create suitable equilibria for the formation of each anion. HpyNbOF 4 (I; py = pyridine) contains the [NbOF4]- anion, while [H2(4,4′-bpy)]NbOF5] (II; 4,4′-bpy = 4,4′-bipyridyl) contains the [NbOF5] 2- anion; their identity is correlated with reagent ratios. The increase of basic species (proton acceptors) results in an increase in the fluoride concentration and high fluoride-containing anions. The crystallization of [NbOF4]- in [NbO2/2F4] ∞ chains in I was controlled with the use of weak base pyridine (pKa = 5.23), while isolated [NbOF5]2- crystallized in II with strong base 4,4′-bipyridyl (pKa = 10.5). This approach can be broadly applied to target-specific basic building units for fundamentally new and potentially functional solid-state materials.",

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AU - Poeppelmeier, Kenneth R.

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From solution to the solid state: Control of niobium oxide-fluoride [NbO_xF_y]^n- species

Abstract

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