RT Journal Article
T1 Pressure-Induced Magnetic Switching and Linkage Isomerism in K0.4Fe4[Cr(CN)6]2.8 · 16H2O: X-ray Absorption and Magnetic Circular Dichroism Studies
A1 Giménez López, María del Carmen
A1 Korzeniak, Tomasz
A1 Levchenko, Georgiy
A1 Romero, Francisco
A1 Segura, Alfredo
A1 Garcia Baonza, Valentin
A1 Cezar, Julio
A1 Milner, Alla
A1 Paz Pasternak, Moshe
A1 Coronado Miralles, Eugenio
A1 Groot, Frank de
K1 Charge transfer
K1 Ions
K1 Isomerization
K1 Magnetic properties
AB The effect of applied pressure on the magnetic properties of the Prussian blue analogueK0.4Fe4[Cr(CN)6]2.8·16H2O (1) has been analyzed by dc and ac magnetic susceptibilitymeasurements. Under ambient conditions, 1 orders ferromagnetically at a critical temperature (TC) of18.5 K. Under application of pressure in the 0−1200 MPa range, the magnetization of the materialdecreases and its critical temperature shifts to lower temperatures, reaching TC = 7.5 K at 1200 MPa.Pressure-dependent Raman and Mössbauer spectroscopy measurements show that this striking behavioris due to the isomerization of some CrIII−C≡N−FeII linkages to the CrIII−N≡C−FeII form. As a result,the ligand field around the iron(II) centers increases, and the diamagnetic low-spin state is populated.As the number of diamagnetic centers in the cubic lattice increases, the net magnetization and criticaltemperature of the material decrease considerably. The phenomenon is reversible: releasing the pressurerestores the magnetic properties of the original material. However, we have found that under moresevere pressure conditions, a metastable sample containing 22% CrIII−N≡C−FeII linkages can beobtained. X-ray absorption spectroscopy and
PB American Chemical Society
SN 0002-7863
YR 2008
FD 2008
LK http://hdl.handle.net/10347/32172
UL http://hdl.handle.net/10347/32172
LA eng
NO Eugenio Coronado, M. Carmen Giménez-López, Tomasz Korzeniak, Georgiy Levchenko, Francisco M. Romero, Alfredo Segura, Valentín García-Baonza, Julio C. Cezar, Frank M. F. de Groot, Alla Milner, and Moshe Paz-Pasternak Journal of the American Chemical Society 2008 130 (46), 15519-15532 DOI: 10.1021/ja8047046
NO This is the Accepted Manuscript of the following article: Coronado, E., Gimenez López, M.C., Korzeniak, T., Levchenko, G., Romero, F.M., Segura, A., García Baonza, V., Cezar, J.C., Groot, F., Milner, A., Paz Pasternak, M., Journal of the American Chemical Society, 2008, DOI:10.1021/ja8047046 CCC
NO We acknowledge financial support from the European Union (NoE Magmanet), the Ministerio de Educación y Ciencia (Projects MAT2004-03849, MAT2007-61584, and CONSOLIDER-INGENIO in Molecular Nanoscience), and Generalitat Valenciana.
DS Minerva
RD 23 abr 2026