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Microscopic Origin for Multistability in a Photomagnetic CoFe Prussian Blue Analogue
Author(s) -
Lejeune Julien,
Cafun JeanDaniel,
Fornasieri Giulia,
Brubach JeanBlaise,
Creff Gaëlle,
Roy Pascale,
Bleuzen Anne
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201200746
Subject(s) - prussian blue , multistability , chemistry , coordination complex , chemical physics , density functional theory , nanotechnology , coordination sphere , metal , crystallography , computational chemistry , crystal structure , electrochemistry , materials science , physics , organic chemistry , electrode , nonlinear system , quantum mechanics
Switchable compounds attract growing interest, as they offer promising perspectives for high‐density storage applications. Much effort has been invested in understanding the mechanisms involved in such properties, in order to prepare systems that are suitable for real applications. Compounds exhibiting an electronic transition that can be triggered by an external stimulus have been extensively studied. While most studies describe the switching properties of such systems in terms of a two‐state model, the existence of multistability in switchable systems remains a controversial topic. In thispaper, we compare the thermally populated Co II Fe III and photoinduced (Co II Fe III )* states of the Na 2 Co 4 [Fe(CN) 6 ] 3.3 · 14H 2 O Prussian blue analogue. The comparison of the infrared spectroscopic data for the two Co II Fe III and (Co II Fe III )* states shows differences at a microscopic scale that cannot be explained in terms of a two‐state model. These experimental data suggest a change in the coordination sphere of the sodium cation, which strongly supports a displacement of the sodium cation in the lattice between the two states. This direct evidence of several distinct CoFe states at an atomic level in this system highlights a new kind of multistability involving competitive metal‐to‐ligand interactions in a switchable compound.