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Título: | The role of order-disorder transitions in the quest for molecular multiferroics: Structural and magnetic neutron studies of a mixed valence iron(II)-iron(III) formate framework |
Autor: | Cañadillas-Delgado, Laura CSIC ORCID; Fabelo, Oscar CSIC ORCID; Rodríguez-Velamazán, J. A. CSIC ORCID; Pardo, Emilio | Fecha de publicación: | 2012 | Editor: | American Chemical Society | Citación: | Journal of the American Chemical Society 134(48): 19772-19781 (2012) | Resumen: | Neutron diffraction studies have been carried out to shed light on the unprecedented order-disorder phase transition (ca. 155 K) observed in the mixed-valence iron(II)-iron(III) formate framework compound [NH 2(CH3)2]n[FeIIIFe II(HCOO)6]n. The crystal structure at 220 K was first determined from Laue diffraction data, then a second refinement at 175 K and the crystal structure determination in the low temperature phase at 45 K were done with data from the monochromatic high resolution single crystal diffractometer D19. The 45 K nuclear structure reveals that the phase transition is associated with the order-disorder of the dimethylammonium counterion that is weakly anchored in the cavities of the [FeIIIFe II(HCOO)6]n framework. In the low-temperature phase, a change in space group from P3Ì„1c to R3Ì„c occurs, involving a tripling of the c-axis due to the ordering of the dimethylammonium counterion. The occurrence of this nuclear phase transition is associated with an electric transition, from paraelectric to antiferroelectric. A combination of powder and single crystal neutron diffraction measurements below the magnetic order transition (ca. 37 K) has been used to determine unequivocally the magnetic structure of this Néel N-Type ferrimagnet, proving that the ferrimagnetic behavior is due to a noncompensation of the different FeII and FeIII magnetic moments. © 2012 American Chemical Society. | URI: | http://hdl.handle.net/10261/74301 | DOI: | 10.1021/ja3082457 | Identificadores: | doi: 10.1021/ja3082457 issn: 0002-7863 e-issn: 1520-5126 |
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