K⊂{[Fe II (Tp)(CN) 3 ] 4 [Co III ( pz Tp)] 3 [Co II ( pz Tp)]}: a neutral soluble model complex of photomagnetic Prussian blue analogues

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.
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D Garnier, J.-R Jim Enez, Yan-Fu Li, J von Bardeleben, Y Journaux, et al.. K⊂{[Fe II (Tp)(CN) 3 ] 4 [Co III ( pz Tp)] 3 [Co II ( pz Tp)]}: a neutral soluble model complex of photomagnetic Prussian blue analogues. Chemical Science , The Royal Society of Chemistry, 2016, 7, pp.4825-4831. ⟨10.1039/c6sc01435f⟩. ⟨hal-01333034⟩

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