Magnetic properties of some transition-metal Prussian Blue Analogs with composition M3[M′(C,N)6]2·xH2O

Heinz Nakotte; Manjita Shrestha; Sourav Adak; Michael Boergert; Vivien S. Zapf; Neil Harrison; Graham King; Luke L. Daemen

doi:10.1016/j.jsamd.2016.06.003

Magnetic properties of some transition-metal Prussian Blue Analogs with composition M₃[M^′(C,N)₆]₂·xH₂O

Heinz Nakotte, Manjita Shrestha, Sourav Adak, Michael Boergert, Vivien S. Zapf, Neil Harrison, Graham King, Luke L. Daemen

Chemical Spectroscopy

Research output: Contribution to journal › Review article › peer-review

17 Scopus citations

Abstract

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 M^IIIN₆ and M^IIC₆ 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.

Original language	English
Pages (from-to)	113-120
Number of pages	8
Journal	Journal of Science: Advanced Materials and Devices
Volume	1
Issue number	2
DOIs	https://doi.org/10.1016/j.jsamd.2016.06.003
State	Published - Jun 2016

Funding

This research was supported by a subcontract between the Los Alamos Neutron Science Center and the Department of Physics, New Mexico State University (Index No: 126767, PI: H. Nakotte). Magnetic studies were performed at the NHMFL Pulsed Field Facility, which is funded by the US National Science Foundation (Grant No. DMR-1157490 ), the State of Florida, and the US Department of Energy . Structure characterization has benefited from the use of HIPD at the Lujan Center at Los Alamos Neutron Science Center, funded by US Department of Energy \u2013 Office of Basic Energy Sciences . Los Alamos National Laboratory is operated by Los Alamos National Security LLC (DoE Contract DE-AC52-06NA25396).

Keywords

Crystal fields
Curie–Weiss behavior
High-spin and low-spin magnetism
Molecular magnetism
Prussian Blue Analogs

Access to Document

10.1016/j.jsamd.2016.06.003

Cite this

@article{754a12b4bca14a84a38bce34d6d170f1,

title = "Magnetic properties of some transition-metal Prussian Blue Analogs with composition M3[M′(C,N)6]2·xH2O",

abstract = "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.",

keywords = "Crystal fields, Curie–Weiss behavior, High-spin and low-spin magnetism, Molecular magnetism, Prussian Blue Analogs",

author = "Heinz Nakotte and Manjita Shrestha and Sourav Adak and Michael Boergert and Zapf, {Vivien S.} and Neil Harrison and Graham King and Daemen, {Luke L.}",

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AU - Nakotte, Heinz

AU - Shrestha, Manjita

AU - Adak, Sourav

AU - Boergert, Michael

AU - Zapf, Vivien S.

AU - Harrison, Neil

AU - King, Graham

AU - Daemen, Luke L.

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N2 - 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.

AB - 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.

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