Magnetic and Optical Bistability Driven by Thermally and Photoinduced Intramolecular Electron Transfer in a Molecular Cobalt-Iron Prussian Blue Analogue

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• 作者：Dongfeng Li ; Rodolphe Cl&eacute ; rac ; Olivier Roubeau ; Etienne Hart&eacute ; Corine Mathoniè ; re ; R&eacute ; my Le Bris ; Stephen M. Holmes
• 刊名：Journal of the American Chemical Society
• 出版年：2008
• 出版时间：January 9, 2008
• 年：2008
• 卷：130
• 期：1
• 页码：252 - 258
• 全文大小：212K
• 年卷期：v.130,no.1(January 9, 2008)
• ISSN：1520-5126

文摘

A soluble molecular analogue of photoresponsive Co/Fe Prussian blues is described within thisreport. As judged via a variety of spectroscopic, magnetic, and crystallographic methods, electron transferwithin the octanuclear complex (below 250 K) converts paramagnetic red crystals into green diamagneticones. The color and magnetic changes are associated with the transformation of Fe^III_LS-CN-Co^II_HS unitsinto Fe^II_LS-CN-Co^III_LS fragments in manner that is identical to that found for the A_n[Co(OH₂)_(6-6m)][Fe(CN)₆]_m·xH₂O(A_n = alkali metal cation) family of three-dimensional Prussian blues. Moreover, this intramolecular electrontransfer can be quantitatively circumvented via rapid thermal quenching and reversed via simple whitelight irradiation at low temperatures. Remarkably the data suggests that thermally or photoinducedparamagnetic metastable phases are identical and exhibit long relaxation times that approach 10 years at120 K.