Next Article in Journal
Modification of TiO2 Nanowire Arrays with Sn Doping as Photoanode for Highly Efficient Dye-Sensitized Solar Cells
Next Article in Special Issue
Molecular Magnets
Previous Article in Journal
A Fast-Response and Helicity-Dependent Lens Enabled by Micro-Patterned Dual-Frequency Liquid Crystals
Previous Article in Special Issue
Thermodynamics and Magnetic Excitations in Quantum Spin Trimers: Applications for the Understanding of Molecular Magnets
Article Menu
Issue 2 (February) cover image

Export Article

Open AccessFeature PaperReview
Crystals 2019, 9(2), 112;

The Effect of Pressure on Magnetic Properties of Prussian Blue Analogues

Technological Laboratory, Department of Magnetism, Institute of Experimental Physics SAS, Watsonova 47, 04001 Kosice, Slovakia
Author to whom correspondence should be addressed.
Received: 8 January 2019 / Revised: 5 February 2019 / Accepted: 16 February 2019 / Published: 20 February 2019
(This article belongs to the Special Issue Molecular Magnets)
PDF [13795 KB, uploaded 20 February 2019]


We present the review of pressure effect on the crystal structure and magnetic properties of Cr(CN)6-based Prussian blue analogues (PBs). The lattice volume of the fcc crystal structure space group Fm 3 ¯ m in the Mn-Cr-CN-PBs linearly decreases for p ≤ 1.7 GPa, the change of lattice size levels off at 3.2 GPa, and above 4.2 GPa an amorphous-like structure appears. The crystal structure recovers after removal of pressure as high as 4.5 GPa. The effect of pressure on magnetic properties follows the non-monotonous pressure dependence of the crystal lattice. The amorphous like structure is accompanied with reduction of the Curie temperature (TC) to zero and a corresponding collapse of the ferrimagnetic moment at 10 GPa. The cell volume of Ni-Cr-CN-PBs decreases linearly and is isotropic in the range of 0–3.1 GPa. The Raman spectra can indicate a weak linkage isomerisation induced by pressure. The Curie temperature in Mn2+-CrIII-PBs and Cr2+-CrIII-PBs with dominant antiferromagnetic super-exchange interaction increases with pressure in comparison with decrease of TC in Ni2+-CrIII-PBs and Co2+-CrIII-PBs ferromagnets. TC increases with increasing pressure for ferrimagnetic systems due to the strengthening of magnetic interaction because pressure, which enlarges the monoelectronic overlap integral S and energy gap ∆ between the mixed molecular orbitals. The reduction of bonding angles between magnetic ions connected by the CN group leads to a small decrease of magnetic coupling. Such a reduction can be expected on both compounds with ferromagnetic and ferrimagnetic ordering. In the second case this effect is masked by the increase of coupling caused by the enlarged overlap between magnetic orbitals. In the case of mixed ferro–ferromagnetic systems, pressure affects μ(T) by a different method in Mn2+–N≡C–CrIII subsystem and CrIII–C≡N–Ni2+ subsystem, and as a consequence Tcomp decreases when the pressure is applied. The pressure changes magnetization processes in both systems, but we expect that spontaneous magnetization is not affected in Mn2+-CrIII-PBs, Ni2+-CrIII-PBs, and Co2+-CrIII-PBs. Pressure-induced magnetic hardening is attributed to a change in magneto-crystalline anisotropy induced by pressure. The applied pressure reduces saturated magnetization of Cr2+-CrIII-PBs. The applied pressure p = 0.84 GPa induces high spin–low spin transition of cca 4.5% of high spin Cr2+. The pressure effect on magnetic properties of PBs nano powders and core–shell heterostructures follows tendencies known from bulk parent PBs. View Full-Text
Keywords: Prussian blue analogues; effect of high pressure; crystal structure; magnetic properties; superexchange interaction Prussian blue analogues; effect of high pressure; crystal structure; magnetic properties; superexchange interaction

Figure 1

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).
Printed Edition Available!
A printed edition of this Special Issue is available here.

Share & Cite This Article

MDPI and ACS Style

Zentkova, M.; Mihalik, M. The Effect of Pressure on Magnetic Properties of Prussian Blue Analogues. Crystals 2019, 9, 112.

Show more citation formats Show less citations formats

Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Related Articles

Article Metrics

Article Access Statistics



[Return to top]
Crystals EISSN 2073-4352 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top