Giménez López, María del CarmenKorzeniak, TomaszLevchenko, GeorgiyRomero, FranciscoSegura, AlfredoGarcia Baonza, ValentinCezar, JulioMilner, AllaPaz Pasternak, MosheCoronado Miralles, EugenioGroot, Frank de2024-02-012024-02-012008Eugenio 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/ja80470460002-7863http://hdl.handle.net/10347/32172This 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 CCCThe effect of applied pressure on the magnetic properties of the Prussian blue analogue K0.4Fe4[Cr(CN)6]2.8·16H2O (1) has been analyzed by dc and ac magnetic susceptibility measurements. Under ambient conditions, 1 orders ferromagnetically at a critical temperature (TC) of 18.5 K. Under application of pressure in the 0−1200 MPa range, the magnetization of the material decreases 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 behavior is 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 critical temperature of the material decrease considerably. The phenomenon is reversible: releasing the pressure restores the magnetic properties of the original material. However, we have found that under more severe pressure conditions, a metastable sample containing 22% CrIII−N≡C−FeII linkages can be obtained. X-ray absorption spectroscopy andengAttribution-NonCommercial-NoDerivatives 4.0 Internacionalhttp://creativecommons.org/licenses/by-nc-nd/4.0/Charge transferIonsIsomerizationMagnetic properties230316 Mecanismos de las reacciones inorgánicas221201 Campos electromagnéticosjournal article10.1021/ja80470461520-5126open access