Magnetic properties of some transition-metal Prussian Blue Analogs with composition M[M(C,N)]·xHO
Abstract
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.
- Authors:
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE; National Science Foundation (NSF)
- OSTI Identifier:
- 1258702
- Alternate Identifier(s):
- OSTI ID: 1345160
- Report Number(s):
- LA-UR-16-25184
Journal ID: ISSN 2468-2179; S2468217916300508; PII: S2468217916300508
- Grant/Contract Number:
- AC52-06NA25396
- Resource Type:
- Published Article
- Journal Name:
- Journal of Science. Advanced Materials and Devices
- Additional Journal Information:
- Journal Name: Journal of Science. Advanced Materials and Devices Journal Volume: 1 Journal Issue: 2; Journal ID: ISSN 2468-2179
- Publisher:
- Elsevier
- Country of Publication:
- Netherlands
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Prussian Blue; metal-organic framework; Prussian Blue Analogs; Curie–Weiss behavior; high-spin and low-spin magnetism; molecular magnetism; crystal fields
Citation Formats
Nakotte, Heinz, Shrestha, Manjita, Adak, Sourav, Boergert, Michael, Zapf, Vivien S., Harrison, Neil, King, Graham, and Daemen, Luke L. Magnetic properties of some transition-metal Prussian Blue Analogs with composition M[M(C,N)]·xHO. Netherlands: N. p., 2016.
Web. doi:10.1016/j.jsamd.2016.06.003.
Nakotte, Heinz, Shrestha, Manjita, Adak, Sourav, Boergert, Michael, Zapf, Vivien S., Harrison, Neil, King, Graham, & Daemen, Luke L. Magnetic properties of some transition-metal Prussian Blue Analogs with composition M[M(C,N)]·xHO. Netherlands. https://doi.org/10.1016/j.jsamd.2016.06.003
Nakotte, Heinz, Shrestha, Manjita, Adak, Sourav, Boergert, Michael, Zapf, Vivien S., Harrison, Neil, King, Graham, and Daemen, Luke L. Wed .
"Magnetic properties of some transition-metal Prussian Blue Analogs with composition M[M(C,N)]·xHO". Netherlands. https://doi.org/10.1016/j.jsamd.2016.06.003.
@article{osti_1258702,
title = {Magnetic properties of some transition-metal Prussian Blue Analogs with composition M[M(C,N)]·xHO},
author = {Nakotte, Heinz and Shrestha, Manjita and Adak, Sourav and Boergert, Michael and Zapf, Vivien S. and Harrison, Neil and King, Graham and Daemen, Luke L.},
abstractNote = {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.},
doi = {10.1016/j.jsamd.2016.06.003},
journal = {Journal of Science. Advanced Materials and Devices},
number = 2,
volume = 1,
place = {Netherlands},
year = {Wed Jun 01 00:00:00 EDT 2016},
month = {Wed Jun 01 00:00:00 EDT 2016}
}
https://doi.org/10.1016/j.jsamd.2016.06.003
Works referenced in this record:
Hydrogen Storage in Prussian Blue Analogues: H 2 Interaction with the Metal Found at the Cavity Surface
journal, January 2010
- Krap, C. P.; Balmaseda, J.; del Castillo, L. F.
- Energy & Fuels, Vol. 24, Issue 1
Control of Charge-Transfer-Induced Spin Transition Temperature on Cobalt−Iron Prussian Blue Analogues
journal, February 2002
- Shimamoto, Naonobu; Ohkoshi, Shin-ichi; Sato, Osamu
- Inorganic Chemistry, Vol. 41, Issue 4
Prussian Blue Analogues for CO2 and SO2 Capture and Separation Applications
journal, June 2010
- Thallapally, Praveen K.; Motkuri, Radha Kishan; Fernandez, Carlos A.
- Inorganic Chemistry, Vol. 49, Issue 11, p. 4909-4915
Prussian Blue and Its Analogues: Electrochemistry and Analytical Applications
journal, June 2001
- Karyakin, Arkady A.
- Electroanalysis, Vol. 13, Issue 10
Thermal expansion in 3d-metal Prussian Blue Analogs—A survey study
journal, November 2011
- Adak, Sourav; Daemen, Luke L.; Hartl, Monika
- Journal of Solid State Chemistry, Vol. 184, Issue 11
Photoinduced Magnetism in a Series of Prussian Blue Analogue Heterostructures
journal, June 2011
- Pajerowski, Daniel M.; Gardner, Justin E.; Frye, Franz A.
- Chemistry of Materials, Vol. 23, Issue 12
Mg3[M(CN)6]2·xH2O with M = Fe, Co: Synthesis, Crystal Structure, and Hydrogen Sorption
journal, May 2012
- Jiménez-Gallegos, Juan; Roque, Jorge; Yee-Madeira, Hernani
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 638, Issue 7-8
Effect of pressure on the magnetic properties of TM 3 [Cr(CN) 6 ] 2 ·12H 2 O
journal, June 2007
- Zentková, M.; Arnold, Z.; Kamarád, J.
- Journal of Physics: Condensed Matter, Vol. 19, Issue 26
Ferromagnetism of the Me 3 (Fe(CN) 6 ) 2 .H 2 O compounds, where Me=Ni and Co
journal, July 1994
- Juszczyk, S.; Johansson, C.; Hanson, M.
- Journal of Physics: Condensed Matter, Vol. 6, Issue 29