Anne Bleuzen

Jean-Blaise Brubach

Julien Lejeune

Pascale Roy

Comptes Rendus Chimie

-Supplementary data- i        Étude structurale des analogues du bleu de Prusse par spectroscopie infra-rouge Application of the infra-red spectroscopy to the structural study of Prussian blue analogues Julien Lejeunea,*, Jean-Blaise Brubachb, Pascale Roya,b, Anne Bleuzena,* a Institut de Chimie Moléculaire et des Matériaux d’Orsay,UMR CNRS 8182, Université Paris-Sud, 15 rue Georges Clémenceau, F-91405 Orsay Cedex, France b Synchrotron SOLEIL, l’Orme des merisiers Saint-Aubin, BP 48, F-91192 Gif-sur-Yvette Cedex, France -Supplementary data- ii   A1. Evolution of the different contributions to the ν{O-H} bands as a function of the chemical composition of AxCoFe PBAs The IR spectrum of PBAs exhibits very sharp bands in the 3550-3700 cm-1 spectral range, associated with water molecules that are not involved in a hydrogen-bonded network. The number of these sharp bands may vary depending on the nature of the PBA (Fig. A1).   Fig. A1. IR spectrum of several AxCoFe PBAs in the spectral range associated with the ν{O-H} vibration band of water molecules bound to the cobalt cations at the Fe(CN)6 vacancies, at T = 300 K. Spectra associated with AxCoFe PBAs exhibiting a CoIIFeIII (resp. CoIIIFeII) ground state at T = 300 K are plotted in red (resp. blue). Legend: K0CoFe (---), Cs0.7CoFe (―·―), Na2CoFe (―), Rb2CoFe (···), Cs2CoFe (―――). The position in term of energy of the main band, associated with the ν{O-H} vibration of water molecules bound to the cobalt cations at the Fe(CN)6 vacancies, mostly depends on the electronic state of the system (and, therefore, of the oxidation state of the cobalt cations): in the -Supplementary data- iii  CoIIFeIII electronic state, the ν{O-H} vibration band associated with water molecules bound to the CoII cations is located above 3638 cm-1; in the CoIIIFeII electronic state, the ν{O-H} vibration band associated with water molecules bound to the CoIII cations is located below 3638 cm-1. The nature and the amount of alkali cations inserted in the structure may modulate the position in terms of energy of this band. 

Application of the infrared spectroscopy to the structural study of Prussian blue analogues

https://comptes-rendus.academie-sciences.fr/chimie/article/10.1016/j.crci.2014.01.017/file/attach/mmc1.pdf

Application of the infrared spectroscopy to the structural study of Prussian blue analogues

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Comptes Rendus Chimie