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Issue 8, 2016
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K⊂{[FeII(Tp)(CN)3]4[CoIII(pzTp)]3[CoII(pzTp)]}: a neutral soluble model complex of photomagnetic Prussian blue analogues

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Abstract

Straightforward access to a new cyanide-bridged {Fe4Co4} “molecular box” containing a potassium ion, namely K⊂{[FeII(Tp)(CN)3]4[CoIII(pzTp)]3[CoII(pzTp)]} (1) (with Tp and pzTp = tris- and tetrakis(pyrazolyl)borate, respectively), is provided, alongside its full characterisation. A detailed analysis of the molecular structure (X-ray diffraction, mass spectrometry, NMR spectroscopy) and electronic properties (EPR spectroscopy, SQUID magnetometry, UV/Vis spectroscopy, cyclic voltammetry) reveals that 1 shows slow magnetic relaxation and a remarkable photomagnetic effect at low temperature which is reminiscent of some FeCo Prussian Blue Analogues (PBAs), and is ascribed to a photo-induced electron transfer. However, in contrast with these inorganic polymers, the overall neutral compound 1 is soluble and remarkably stable in organic solvents such as CH2Cl2. Moreover, 1 shows interesting redox versatility, with electrochemical experiments revealing the possible access to six stable redox states.

Graphical abstract: K⊂{[FeII(Tp)(CN)3]4[CoIII(pzTp)]3[CoII(pzTp)]}: a neutral soluble model complex of photomagnetic Prussian blue analogues

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Publication details

The article was received on 01 Apr 2016, accepted on 13 May 2016 and first published on 13 May 2016


Article type: Edge Article
DOI: 10.1039/C6SC01435F
Citation: Chem. Sci., 2016,7, 4825-4831
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    K⊂{[FeII(Tp)(CN)3]4[CoIII(pzTp)]3[CoII(pzTp)]}: a neutral soluble model complex of photomagnetic Prussian blue analogues

    D. Garnier, J.-R. Jiménez, Y. Li, J. von Bardeleben, Y. Journaux, T. Augenstein, E. M. B. Moos, M. T. Gamer, F. Breher and R. Lescouëzec, Chem. Sci., 2016, 7, 4825
    DOI: 10.1039/C6SC01435F

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