TY - JOUR
T1 - 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)
AU - Torres, Neil
AU - Osiry, Hernández
AU - Rodríguez, Alejandro
AU - Martínez-Dlcruz, Lorena
AU - Lemus-Santana, Ana A.
AU - Reguera, Edilso
N1 - Publisher Copyright:
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2018/5/17
Y1 - 2018/5/17
N2 - 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.
AB - 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.
KW - Dipole
KW - Dipole interaction
KW - Hydrogen bond bridges
KW - Hydrogen storage
KW - Molecular magnet
KW - Quadrupole interaction
KW - Vanadium
KW - Vanadyl prussian blue analogue
UR - http://www.scopus.com/inward/record.url?scp=85054692186&partnerID=8YFLogxK
U2 - 10.1002/zaac.201700450
DO - 10.1002/zaac.201700450
M3 - Artículo
SN - 0044-2313
VL - 644
SP - 415
EP - 423
JO - Zeitschrift fur Anorganische und Allgemeine Chemie
JF - Zeitschrift fur Anorganische und Allgemeine Chemie
IS - 8-9
ER -