Photomagnetism in CxCo4[Fe(CN)6](8+x)/3·n H2O Prussian blue analogues: looking for the maximum photo-efficiency
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- 作者：Bleuzen ; Anne ; Escax ; Virginie ; Itié ; Jean-Paul ; Mü ; nsch ; Pascal ; Verdaguer ; Michel
- 关键词：Prussian blue analogues ; photomagnetism ; electron transfer ; X-ray diffraction ; analogues du bleu de Prusse ; photomagné ; tisme ; transfert d’ ; é ; lectron ; diffraction des rayons X
- 刊名：Comptes Rendus Chimie
- 出版年：2003
- 出版时间：March, 2003
- 年：2003
- 卷：6
- 期：3
- 页码：343-352
- 全文大小：175 K
文摘
A family of CoFe Prussian blue analogues CxCo4[Fe(CN)6](8+x/3)
(4–x)3 (x = amount of alkali cation inserted per conventional cell, C = Na, K, Rb, Cs; = [Fe(CN)6] vacancy) have been synthesized and characterized. Their photomagnetic properties have been investigated by magnetic measurements before and after irradiation and X-ray diffraction under continuous irradiation. We show that the photo-induced magnetism depends on several parameters: (i) the amount of CoIII–FeII diamagnetic excitable pairs per cell; (ii) the amount of [Fe(CN)6] vacancies, and (iii) the amount and nature of the alkali cations per cell. We evidence a discontinuity in the properties' change when the amount of alkali cation x varies, around x = 1. For x < 1, there is an excitation of diluted CoIII–FeII diamagnetic pairs in a phase mainly composed of magnetic CoII–FeIII entities within the same structural phase through a second-order continuous transformation. For x ≥ 1, the formation of domains mainly composed of CoII–FeIII* metastable magnetic pairs in a phase mainly composed of CoIII–FeII diamagnetic ones through a first-order discontinuous transition is observed. The study points out that sodium derivatives are more efficient than the others. Among them, Na1Co4[Fe(CN)6]31 is predicted to be the most efficient one. To cite this article: A. Bleuzen et al., C. R. Chimie 6 (2003).
(4–x)3 (x = amount of alkali cation inserted per conventional cell, C = Na, K, Rb, Cs; = [Fe(CN)6] vacancy) have been synthesized and characterized. Their photomagnetic properties have been investigated by magnetic measurements before and after irradiation and X-ray diffraction under continuous irradiation. We show that the photo-induced magnetism depends on several parameters: (i) the amount of CoIII–FeII diamagnetic excitable pairs per cell; (ii) the amount of [Fe(CN)6] vacancies, and (iii) the amount and nature of the alkali cations per cell. We evidence a discontinuity in the properties' change when the amount of alkali cation x varies, around x = 1. For x < 1, there is an excitation of diluted CoIII–FeII diamagnetic pairs in a phase mainly composed of magnetic CoII–FeIII entities within the same structural phase through a second-order continuous transformation. For x ≥ 1, the formation of domains mainly composed of CoII–FeIII* metastable magnetic pairs in a phase mainly composed of CoIII–FeII diamagnetic ones through a first-order discontinuous transition is observed. The study points out that sodium derivatives are more efficient than the others. Among them, Na1Co4[Fe(CN)6]31 is predicted to be the most efficient one. To cite this article: A. Bleuzen et al., C. R. Chimie 6 (2003).