TY - JOUR
T1 - From solution to the solid state
T2 - Control of niobium oxide-fluoride [NbOxFy]n- species
AU - Lu, Hongcheng
AU - Gautier, Romain
AU - Donakowski, Martin D.
AU - Liu, Zhengtang
AU - Poeppelmeier, Kenneth R.
PY - 2014/1/6
Y1 - 2014/1/6
N2 - 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.
AB - 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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U2 - 10.1021/ic402561g
DO - 10.1021/ic402561g
M3 - Article
AN - SCOPUS:84891773371
VL - 53
SP - 537
EP - 542
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 1
ER -