129Xe NMR spectroscopy study of porous cyanometallates

E. Lima, J. Balmaseda, E. Reguera

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Abstract

Zinc and cadmium hexacyanocobaltates(III) were prepared, and their porous networks were explored using 129 Xe spectroscopy. The crystal structures of these two compounds are representative of porous hexacyanometallates, cubic (Fm-3m) for cadmium and rhombohedral (R-3c) for zinc. In the cubic structure, the porosity is related to systematic vacancies created from the elemental building block (i.e., the hexacyanometallate anion), whereas the rhombohedral (R-3c) structure is free of vacant sites but has tetrahedral coordination for the zinc atom, which leads to relatively large ellipsoidal pores communicated by elliptical windows. According to the Xe adsorption isotherms, these porous frameworks were found to be accessible to the Xe atom. The structure of the higher electric field gradient at the pore surface (Fm-3m) appears and is accompanied by a stronger guest-host interaction for the Xe atoms and a higher capacity for Xe sorption. For cadmium, the 129 Xe NMR signal is typical of isotropic movement for the Xe atom, indicating that it remains trapped within a spherical cavity. From spectra recorded for different amounts of adsorbed Xe, the cavity diameter was estimated. For the zinc complex, 129 Xe NMR spectra are asymmetric because of the Xe atom movement within an elongated cavity. The line-shape asymmetry changes when the Xe loading within the porous framework increases, which was ascribed to Xe-Xe interactions through the cavity windows. The Xe adsorption revealed additional structural information for the studied materials. © 2007 American Chemical Society.
Original languageAmerican English
Pages (from-to)5752-5756
Number of pages5
JournalLangmuir
DOIs
StatePublished - 8 May 2007
Externally publishedYes

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Nuclear magnetic resonance spectroscopy
Zinc
Atoms
nuclear magnetic resonance
zinc
Cadmium
cadmium
cavities
spectroscopy
atoms
porosity
Nuclear magnetic resonance
adsorption
Adsorption isotherms
sorption
Vacancies
Anions
line shape
Sorption
isotherms

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Lima, E. ; Balmaseda, J. ; Reguera, E. / 129Xe NMR spectroscopy study of porous cyanometallates. In: Langmuir. 2007 ; pp. 5752-5756.
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abstract = "Zinc and cadmium hexacyanocobaltates(III) were prepared, and their porous networks were explored using 129 Xe spectroscopy. The crystal structures of these two compounds are representative of porous hexacyanometallates, cubic (Fm-3m) for cadmium and rhombohedral (R-3c) for zinc. In the cubic structure, the porosity is related to systematic vacancies created from the elemental building block (i.e., the hexacyanometallate anion), whereas the rhombohedral (R-3c) structure is free of vacant sites but has tetrahedral coordination for the zinc atom, which leads to relatively large ellipsoidal pores communicated by elliptical windows. According to the Xe adsorption isotherms, these porous frameworks were found to be accessible to the Xe atom. The structure of the higher electric field gradient at the pore surface (Fm-3m) appears and is accompanied by a stronger guest-host interaction for the Xe atoms and a higher capacity for Xe sorption. For cadmium, the 129 Xe NMR signal is typical of isotropic movement for the Xe atom, indicating that it remains trapped within a spherical cavity. From spectra recorded for different amounts of adsorbed Xe, the cavity diameter was estimated. For the zinc complex, 129 Xe NMR spectra are asymmetric because of the Xe atom movement within an elongated cavity. The line-shape asymmetry changes when the Xe loading within the porous framework increases, which was ascribed to Xe-Xe interactions through the cavity windows. The Xe adsorption revealed additional structural information for the studied materials. {\circledC} 2007 American Chemical Society.",
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129Xe NMR spectroscopy study of porous cyanometallates. / Lima, E.; Balmaseda, J.; Reguera, E.

In: Langmuir, 08.05.2007, p. 5752-5756.

Research output: Contribution to journalArticleResearchpeer-review

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AU - Balmaseda, J.

AU - Reguera, E.

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N2 - Zinc and cadmium hexacyanocobaltates(III) were prepared, and their porous networks were explored using 129 Xe spectroscopy. The crystal structures of these two compounds are representative of porous hexacyanometallates, cubic (Fm-3m) for cadmium and rhombohedral (R-3c) for zinc. In the cubic structure, the porosity is related to systematic vacancies created from the elemental building block (i.e., the hexacyanometallate anion), whereas the rhombohedral (R-3c) structure is free of vacant sites but has tetrahedral coordination for the zinc atom, which leads to relatively large ellipsoidal pores communicated by elliptical windows. According to the Xe adsorption isotherms, these porous frameworks were found to be accessible to the Xe atom. The structure of the higher electric field gradient at the pore surface (Fm-3m) appears and is accompanied by a stronger guest-host interaction for the Xe atoms and a higher capacity for Xe sorption. For cadmium, the 129 Xe NMR signal is typical of isotropic movement for the Xe atom, indicating that it remains trapped within a spherical cavity. From spectra recorded for different amounts of adsorbed Xe, the cavity diameter was estimated. For the zinc complex, 129 Xe NMR spectra are asymmetric because of the Xe atom movement within an elongated cavity. The line-shape asymmetry changes when the Xe loading within the porous framework increases, which was ascribed to Xe-Xe interactions through the cavity windows. The Xe adsorption revealed additional structural information for the studied materials. © 2007 American Chemical Society.

AB - Zinc and cadmium hexacyanocobaltates(III) were prepared, and their porous networks were explored using 129 Xe spectroscopy. The crystal structures of these two compounds are representative of porous hexacyanometallates, cubic (Fm-3m) for cadmium and rhombohedral (R-3c) for zinc. In the cubic structure, the porosity is related to systematic vacancies created from the elemental building block (i.e., the hexacyanometallate anion), whereas the rhombohedral (R-3c) structure is free of vacant sites but has tetrahedral coordination for the zinc atom, which leads to relatively large ellipsoidal pores communicated by elliptical windows. According to the Xe adsorption isotherms, these porous frameworks were found to be accessible to the Xe atom. The structure of the higher electric field gradient at the pore surface (Fm-3m) appears and is accompanied by a stronger guest-host interaction for the Xe atoms and a higher capacity for Xe sorption. For cadmium, the 129 Xe NMR signal is typical of isotropic movement for the Xe atom, indicating that it remains trapped within a spherical cavity. From spectra recorded for different amounts of adsorbed Xe, the cavity diameter was estimated. For the zinc complex, 129 Xe NMR spectra are asymmetric because of the Xe atom movement within an elongated cavity. The line-shape asymmetry changes when the Xe loading within the porous framework increases, which was ascribed to Xe-Xe interactions through the cavity windows. The Xe adsorption revealed additional structural information for the studied materials. © 2007 American Chemical Society.

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