4.8 Article

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

Journal

CHEMICAL SCIENCE
Volume 7, Issue 8, Pages 4825-4831

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/c6sc01435f

Keywords

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Funding

  1. DFG [B4, SFB/TRR 88]
  2. Ministere de l'Enseignement et de la Recherche
  3. Centre National de la Recherche Scientifique
  4. Agence National de la Recherche (MoMa project) [ANR-14-JTIC-0001]
  5. Agence Nationale de la Recherche (ANR) [ANR-14-JTIC-0001] Funding Source: Agence Nationale de la Recherche (ANR)

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Straightforward access to a new cyanide-bridged {Fe4Co4} molecular box containing a potassium ion, namely K subset of{[Fe-II(Tp)(CN)(3)](4)[Co-III((pz)Tp)](3)[Co-II((pz)Tp)]} (1) ( with Tp and (pz)Tp = 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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