TY - JOUR
T1 - Hydrothermal Recrystallization as a Strategy to Reveal the Structural Diversity in Hexacyanometallates
T2 - Nickel and Copper Hexacyanoosmates(II)
AU - Reguera, Leslie
AU - López, Noeldris L.
AU - Rodríguez-Hernández, Joelis
AU - Martínez-García, Ricardo
AU - Reguera, Edilso
N1 - Publisher Copyright:
© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2020/5/14
Y1 - 2020/5/14
N2 - The results discussed herein reinforce the relevance of the hydrothermal recrystallization in transition metal hexacyanometallates as a suitable strategy to access the structural diversity of this family of coordination polymers. Copper(2+) and nickel(2+) hexacyanoosmates(II) were prepared by the precipitation method using hexacyanoosmic(II) acid as the complex anion source, obtaining powders of insufficient crystalline quality for the structural study. These powders were then recrystallized under hydrothermal conditions. For Ni, three new phases where formed, monoclinic and tetragonal, and a hexagonal modification when the monoclinic one is dehydrated under soft heating. For copper, one new tetragonal phase was found, in addition to the previously reported cubic one, typical of Prussian blue analogues. The crystal structure for these four nickel and cooper hexacyanoosmates(II) were solved and refined ab initio from powder XRD data. The refined crystal structures are properly supported by a detailed spectroscopic study from IR and UV/Vis data, Ligand Field Analysis, and thermal, magnetic and hydrogen adsorption measurements. In the anhydrous phase for nickel, neighboring Ni atoms were found coordinated by bifurcated N end, an atypical coordination mode for the CN– ligand. The results herein discussed contribute to shed light on the vast information unrevealed on the coordination chemistry of transition metal hexacyanometallates.
AB - The results discussed herein reinforce the relevance of the hydrothermal recrystallization in transition metal hexacyanometallates as a suitable strategy to access the structural diversity of this family of coordination polymers. Copper(2+) and nickel(2+) hexacyanoosmates(II) were prepared by the precipitation method using hexacyanoosmic(II) acid as the complex anion source, obtaining powders of insufficient crystalline quality for the structural study. These powders were then recrystallized under hydrothermal conditions. For Ni, three new phases where formed, monoclinic and tetragonal, and a hexagonal modification when the monoclinic one is dehydrated under soft heating. For copper, one new tetragonal phase was found, in addition to the previously reported cubic one, typical of Prussian blue analogues. The crystal structure for these four nickel and cooper hexacyanoosmates(II) were solved and refined ab initio from powder XRD data. The refined crystal structures are properly supported by a detailed spectroscopic study from IR and UV/Vis data, Ligand Field Analysis, and thermal, magnetic and hydrogen adsorption measurements. In the anhydrous phase for nickel, neighboring Ni atoms were found coordinated by bifurcated N end, an atypical coordination mode for the CN– ligand. The results herein discussed contribute to shed light on the vast information unrevealed on the coordination chemistry of transition metal hexacyanometallates.
KW - Copper
KW - Hexacyanometallates
KW - Nickel
KW - Optical properties
KW - Prussian blue analogues
KW - Structure elucidation
UR - http://www.scopus.com/inward/record.url?scp=85084528426&partnerID=8YFLogxK
U2 - 10.1002/ejic.202000086
DO - 10.1002/ejic.202000086
M3 - Artículo
SN - 1434-1948
VL - 2020
SP - 1763
EP - 1774
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 18
ER -