On the origin of the differences in structure directing properties of polar metal oxyfluoride [MOxF6-x]2- (x = 1, 2) building units

Romain Gautier, Régis Gautier, Kelvin B. Chang, Kenneth R Poeppelmeier

Research output: Contribution to journalArticle

23 Citations (Scopus)

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 languageEnglish
Pages (from-to)1712-1719
Number of pages8
JournalInorganic Chemistry
Volume54
Issue number4
DOIs
Publication statusPublished - Feb 16 2015

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oxyfluorides
Anions
Metals
anions
orbitals
metals
Inorganic compounds
inorganic compounds
Crystallization
Discrete Fourier transforms
Transition metals
Hydrogen bonds
Crystal structure
transition metals
interactions
chemistry
crystallization
hydrogen bonds
Ligands
solid state

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 journalArticle

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