Synthesis, Crystal Structures, and Properties of Zeolite-Like T<inf>3</inf>(H<inf>3</inf>O)<inf>2</inf>[M(CN)<inf>6</inf>]<inf>2</inf>·uH<inf>2</inf>O (T = Co, Zn; M = Ru, Os)

Leslie Reguera, Noeldris L. López, Joelis Rodríguez-Hernández, Marlene González, Carlos E. Hernandez-Tamargo, David Santos-Carballal, Nora H. de Leeuw, Edilso Reguera

Research output: Contribution to journalArticle

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Abstract

© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim We report the synthesis, crystal structures, and related properties of six new zeolite-like hexacyanometallates of formula unit T3(H3O)2[M(CN)6]2·uH2O (T = Co2+, Zn2+; M = RuII, OsII). Their crystal structures were solved and refined from their X-ray powder diffraction patterns in combination with the IR and UV/Vis/NIR spectroscopic data. The Co and Zn ions are coordinated tetrahedrally to the N atoms of four CN groups. The deconvolution of the overlapped UV/Vis/NIR spectral bands provided conclusive evidence of the tetrahedral coordination of the Co atoms. These materials have porous frameworks, which are characterized by a 3D array of TN4 tetrahedral units linked to the MC6 octahedral blocks in a 3:2 ratio. From the IR spectroscopy results, we found that all of the compounds reported here contain hydronium countercations. Two different structures in the same space group (R3c) were identified for the Co-based materials. However, only a single phase was found for the Zn-containing compounds. Density functional theory (DFT) modeling predicts hydrogen bonds between the hydronium ions and the CN groups at the surfaces of the pores. These materials were prepared through the hydrothermal recrystallization of the solids obtained from mixing ethanol solutions of H4[M(CN)6] with aqueous solutions of cobalt(II) nitrate and zinc nitrate. Our results illustrate the potential of the hydrothermal recrystallization technique for the preparation of metal hexacyanometallates with new structures and pore topologies that are not obtainable by the traditional precipitation method.
Original languageAmerican English
Pages (from-to)2980-2989
Number of pages2681
JournalEuropean Journal of Inorganic Chemistry
DOIs
StatePublished - 23 Jun 2017

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Zeolites
Crystal structure
Atoms
Deconvolution
Cobalt
X ray powder diffraction
Diffraction patterns
Density functional theory
Porous materials
Infrared spectroscopy
Nitrates
Hydrogen bonds
Ethanol
Crystallization
Metals
Topology
Ions
zinc nitrate
hydronium ion

Cite this

Reguera, Leslie ; López, Noeldris L. ; Rodríguez-Hernández, Joelis ; González, Marlene ; Hernandez-Tamargo, Carlos E. ; Santos-Carballal, David ; de Leeuw, Nora H. ; Reguera, Edilso. / Synthesis, Crystal Structures, and Properties of Zeolite-Like T<inf>3</inf>(H<inf>3</inf>O)<inf>2</inf>[M(CN)<inf>6</inf>]<inf>2</inf>·uH<inf>2</inf>O (T = Co, Zn; M = Ru, Os). In: European Journal of Inorganic Chemistry. 2017 ; pp. 2980-2989.
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Synthesis, Crystal Structures, and Properties of Zeolite-Like T<inf>3</inf>(H<inf>3</inf>O)<inf>2</inf>[M(CN)<inf>6</inf>]<inf>2</inf>·uH<inf>2</inf>O (T = Co, Zn; M = Ru, Os). / Reguera, Leslie; López, Noeldris L.; Rodríguez-Hernández, Joelis; González, Marlene; Hernandez-Tamargo, Carlos E.; Santos-Carballal, David; de Leeuw, Nora H.; Reguera, Edilso.

In: European Journal of Inorganic Chemistry, 23.06.2017, p. 2980-2989.

Research output: Contribution to journalArticle

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T1 - Synthesis, Crystal Structures, and Properties of Zeolite-Like T3(H3O)2[M(CN)6]2·uH2O (T = Co, Zn; M = Ru, Os)

AU - Reguera, Leslie

AU - López, Noeldris L.

AU - Rodríguez-Hernández, Joelis

AU - González, Marlene

AU - Hernandez-Tamargo, Carlos E.

AU - Santos-Carballal, David

AU - de Leeuw, Nora H.

AU - Reguera, Edilso

PY - 2017/6/23

Y1 - 2017/6/23

N2 - © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim We report the synthesis, crystal structures, and related properties of six new zeolite-like hexacyanometallates of formula unit T3(H3O)2[M(CN)6]2·uH2O (T = Co2+, Zn2+; M = RuII, OsII). Their crystal structures were solved and refined from their X-ray powder diffraction patterns in combination with the IR and UV/Vis/NIR spectroscopic data. The Co and Zn ions are coordinated tetrahedrally to the N atoms of four CN groups. The deconvolution of the overlapped UV/Vis/NIR spectral bands provided conclusive evidence of the tetrahedral coordination of the Co atoms. These materials have porous frameworks, which are characterized by a 3D array of TN4 tetrahedral units linked to the MC6 octahedral blocks in a 3:2 ratio. From the IR spectroscopy results, we found that all of the compounds reported here contain hydronium countercations. Two different structures in the same space group (R3c) were identified for the Co-based materials. However, only a single phase was found for the Zn-containing compounds. Density functional theory (DFT) modeling predicts hydrogen bonds between the hydronium ions and the CN groups at the surfaces of the pores. These materials were prepared through the hydrothermal recrystallization of the solids obtained from mixing ethanol solutions of H4[M(CN)6] with aqueous solutions of cobalt(II) nitrate and zinc nitrate. Our results illustrate the potential of the hydrothermal recrystallization technique for the preparation of metal hexacyanometallates with new structures and pore topologies that are not obtainable by the traditional precipitation method.

AB - © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim We report the synthesis, crystal structures, and related properties of six new zeolite-like hexacyanometallates of formula unit T3(H3O)2[M(CN)6]2·uH2O (T = Co2+, Zn2+; M = RuII, OsII). Their crystal structures were solved and refined from their X-ray powder diffraction patterns in combination with the IR and UV/Vis/NIR spectroscopic data. The Co and Zn ions are coordinated tetrahedrally to the N atoms of four CN groups. The deconvolution of the overlapped UV/Vis/NIR spectral bands provided conclusive evidence of the tetrahedral coordination of the Co atoms. These materials have porous frameworks, which are characterized by a 3D array of TN4 tetrahedral units linked to the MC6 octahedral blocks in a 3:2 ratio. From the IR spectroscopy results, we found that all of the compounds reported here contain hydronium countercations. Two different structures in the same space group (R3c) were identified for the Co-based materials. However, only a single phase was found for the Zn-containing compounds. Density functional theory (DFT) modeling predicts hydrogen bonds between the hydronium ions and the CN groups at the surfaces of the pores. These materials were prepared through the hydrothermal recrystallization of the solids obtained from mixing ethanol solutions of H4[M(CN)6] with aqueous solutions of cobalt(II) nitrate and zinc nitrate. Our results illustrate the potential of the hydrothermal recrystallization technique for the preparation of metal hexacyanometallates with new structures and pore topologies that are not obtainable by the traditional precipitation method.

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