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

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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
Issue number4
Publication statusPublished - Feb 16 2015


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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