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Title: Magnetic properties of some transition-metal Prussian Blue Analogs with composition M[M(C,N)]·xHO

Journal Article · · Journal of Science. Advanced Materials and Devices
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Here, magnetic data are reported for Prussian Blue Analogs (PBAs) of composition M3[M'(C,N)6]2·xH2O, where M = Mn, Co, Ni or Cu and M' = Cr, Fe or Co and x is the number of water molecules per unit cell. PBAs crystallize in cubic framework structures, which consist of alternating MIIIN6 and MIIC6 octahedra. Occupancies of the octrahedra are not perfect: they may be empty and the charges are balanced by the oxygen atoms originating from guest water molecules at the lattice site (C or N site) or the interstitial site (between the octahedrals) of the unit cell. Large crystal-field splittings due to the octrahedral environment results in a combination of low- or high-spin configurations of localized magnetic bivalent and trivalent 3d moments. The magnetic susceptibility of studied PBAs follows the Curie–Weiss behavior in the paramagnetic region up to room temperature. Moreover, the data provide evidence for a long-range magnetic ground state for most metal hexacyanochromates and all metal hexacyanoferrates, while hexacyanocobaltates remain paramagnetic down to the lowest temperature measured (2 K). For all compounds, the effective magnetic moments determined from experiments were found to be in reasonable agreement with predicted combinations of high- and low-spin moments.

Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE; National Science Foundation (NSF)
Grant/Contract Number:
AC52-06NA25396
OSTI ID:
1258702
Alternate ID(s):
OSTI ID: 1345160
Report Number(s):
LA-UR-16-25184; S2468217916300508; PII: S2468217916300508
Journal Information:
Journal of Science. Advanced Materials and Devices, Journal Name: Journal of Science. Advanced Materials and Devices Vol. 1 Journal Issue: 2; ISSN 2468-2179
Publisher:
ElsevierCopyright Statement
Country of Publication:
Netherlands
Language:
English

References (9)

Hydrogen Storage in Prussian Blue Analogues: H 2 Interaction with the Metal Found at the Cavity Surface journal January 2010
Control of Charge-Transfer-Induced Spin Transition Temperature on Cobalt−Iron Prussian Blue Analogues journal February 2002
Prussian Blue Analogues for CO2 and SO2 Capture and Separation Applications journal June 2010
Prussian Blue and Its Analogues: Electrochemistry and Analytical Applications journal June 2001
Thermal expansion in 3d-metal Prussian Blue Analogs—A survey study journal November 2011
Photoinduced Magnetism in a Series of Prussian Blue Analogue Heterostructures journal June 2011
Mg3[M(CN)6]2·xH2O with M = Fe, Co: Synthesis, Crystal Structure, and Hydrogen Sorption journal May 2012
Effect of pressure on the magnetic properties of TM 3 [Cr(CN) 6 ] 2 ·12H 2 O journal June 2007
Ferromagnetism of the Me 3 (Fe(CN) 6 ) 2 .H 2 O compounds, where Me=Ni and Co journal July 1994

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Related Subjects

36 MATERIALS SCIENCE
Prussian Blue
metal-organic framework
Prussian Blue Analogs
Curie–Weiss behavior
high-spin and low-spin magnetism
molecular magnetism
crystal fields