Abstract
In oxyfluoride chemistry, the [MOxF6-x]2- anions (M = transition metal) are interesting polar building units that may be used to design polar materials, but their polar vs antipolar orientations in the solid state, which directly depend on the interactions between O2-/F- ligands and the extended structure, remain difficult to control. To improve this control, these interactions were assessed through crystallization of five related [MOxF6-x]2- (M = Ti4+, V5+, Mo6+, W6+) anions with organic molecules. The hybrid organic-inorganic compounds, (4,4′-bpyH2)TiF6 (1), (enH2)MoO2F4 (2), (4-hpyH)2MoO2F4·H2O (3), (4,4′-bpyH2)WO2F4 (4), and (4,4′-bpyH2)VOF5 (5), exhibit isolated [MOxF6-x]2- anions in a hydrogen bond network. The analysis of these crystal structures in combination with DFT calculations elucidate how differences in structure directing properties of these anions arise when π-overlap between O 2p orbitals and M d orbitals is weak and significantly affected by an increase of the energy of the d orbitals from 3d to 5d.
| Original language | English |
|---|---|
| Pages (from-to) | 1712-1719 |
| Number of pages | 8 |
| Journal | Inorganic Chemistry |
| Volume | 54 |
| Issue number | 4 |
| DOIs | |
| Publication status | Published - Feb 16 2015 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Physical and Theoretical Chemistry
Cite this
On the origin of the differences in structure directing properties of polar metal oxyfluoride [MOxF6-x]2- (x = 1, 2) building units. / Gautier, Romain; Gautier, Régis; Chang, Kelvin B.; Poeppelmeier, Kenneth R.
In: Inorganic Chemistry, Vol. 54, No. 4, 16.02.2015, p. 1712-1719.Research output: Contribution to journal › Article
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TY - JOUR
T1 - On the origin of the differences in structure directing properties of polar metal oxyfluoride [MOxF6-x]2- (x = 1, 2) building units
AU - Gautier, Romain
AU - Gautier, Régis
AU - Chang, Kelvin B.
AU - Poeppelmeier, Kenneth R
PY - 2015/2/16
Y1 - 2015/2/16
N2 - In oxyfluoride chemistry, the [MOxF6-x]2- anions (M = transition metal) are interesting polar building units that may be used to design polar materials, but their polar vs antipolar orientations in the solid state, which directly depend on the interactions between O2-/F- ligands and the extended structure, remain difficult to control. To improve this control, these interactions were assessed through crystallization of five related [MOxF6-x]2- (M = Ti4+, V5+, Mo6+, W6+) anions with organic molecules. The hybrid organic-inorganic compounds, (4,4′-bpyH2)TiF6 (1), (enH2)MoO2F4 (2), (4-hpyH)2MoO2F4·H2O (3), (4,4′-bpyH2)WO2F4 (4), and (4,4′-bpyH2)VOF5 (5), exhibit isolated [MOxF6-x]2- anions in a hydrogen bond network. The analysis of these crystal structures in combination with DFT calculations elucidate how differences in structure directing properties of these anions arise when π-overlap between O 2p orbitals and M d orbitals is weak and significantly affected by an increase of the energy of the d orbitals from 3d to 5d.
AB - In oxyfluoride chemistry, the [MOxF6-x]2- anions (M = transition metal) are interesting polar building units that may be used to design polar materials, but their polar vs antipolar orientations in the solid state, which directly depend on the interactions between O2-/F- ligands and the extended structure, remain difficult to control. To improve this control, these interactions were assessed through crystallization of five related [MOxF6-x]2- (M = Ti4+, V5+, Mo6+, W6+) anions with organic molecules. The hybrid organic-inorganic compounds, (4,4′-bpyH2)TiF6 (1), (enH2)MoO2F4 (2), (4-hpyH)2MoO2F4·H2O (3), (4,4′-bpyH2)WO2F4 (4), and (4,4′-bpyH2)VOF5 (5), exhibit isolated [MOxF6-x]2- anions in a hydrogen bond network. The analysis of these crystal structures in combination with DFT calculations elucidate how differences in structure directing properties of these anions arise when π-overlap between O 2p orbitals and M d orbitals is weak and significantly affected by an increase of the energy of the d orbitals from 3d to 5d.
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U2 - 10.1021/ic5026735
DO - 10.1021/ic5026735
M3 - Article
VL - 54
SP - 1712
EP - 1719
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 4
ER -