TY - JOUR
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
N1 - Publisher Copyright:
© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017
Y1 - 2017
N2 - 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 - 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.
KW - Cyanides
KW - Osmium
KW - Porous solids
KW - Ruthenium
KW - Structure elucidation
KW - Zeolite analogues
UR - http://www.scopus.com/inward/record.url?scp=85021152059&partnerID=8YFLogxK
U2 - 10.1002/ejic.201700278
DO - 10.1002/ejic.201700278
M3 - Artículo
SN - 1434-1948
VL - 2017
SP - 2980
EP - 2989
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 23
ER -