Unusually strong dipole–dipole and dipole–quadrupole interactions in a nanoporous solid. Crystal structure and related properties of (vo)3[m(cn)6]2·nh2o (m = fe, co)

Neil Torres, Hernández Osiry, Alejandro Rodríguez, Lorena Martínez-Dlcruz, Ana A. Lemus-Santana, Edilso Reguera

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

Abstract

In porous Prussian blue (PB) analogues, the partially naked central metal atoms found at the cavities surface are responsible for many of their physical properties, among them the adsorption potentials. In the as-synthesized PB analogues, such metal sites stabilize water molecules inside the cavity through coordination bond formation. The filling of the cavity volume is completed with water molecules linked to the coordinated ones through hydrogen bonds formation. Vanadyl-based PB analogue shows quite different features. The metal(V) at the cavities surface has saturated its coordination sphere with the O atom of the vanadyl ion (V=O). In this material, the V=O group preserves enough strong dipole moment to stabilize adsorbed species at the cavity through dipole–dipole and dipole–quadrupole in-teractions. This contribution reports the preparation, crystal structure and properties for (VO)3[M(CN)6]2·nH2O (M = Fe, Co). According to the refined crystal structure, IR spectra and TG data, six water molecules remain stabilized inside the cavities through a strong dipole– dipole coupling with the vanadyl group. The cavity contains additional water molecules interacting through hydrogen bond bridges with the water molecules coupled to the V=O group. The vanadyl ion is free of hydrogen bonding interactions with the water molecules. The recorded adsorption isotherms for N2, CO2 and H2, three molecules with only quadrupole moment, reveal presence of relative strong adsorption forces due to dipole-quadrupole interactions.

Original languageEnglish
Pages (from-to)415-423
Number of pages9
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Volume644
Issue number8-9
DOIs
StatePublished - 17 May 2018

Keywords

  • Dipole
  • Dipole interaction
  • Hydrogen bond bridges
  • Hydrogen storage
  • Molecular magnet
  • Quadrupole interaction
  • Vanadium
  • Vanadyl prussian blue analogue

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