Whereas there are hundreds of known iron(II) spin-crossover compounds, only a handful of cobalt(II) spin-crossover compounds have been discovered to date, and hardly an in depth study on any of them exists. This review begins with an introduction into the theoretical aspects to be considered when discussing spin-crossover compounds in general and cobalt(II) systems in particular. It is followed by case studies on [Co(bpy)3]2+ and [Co(terpy)2]2+ (bpy = 2,2′-bipyridine, terpy = 2,2′:6′,2″-terpyridine) presenting and discussing results from magnetic susceptibility measurements, X-ray crystallography, optical spectroscopy, and EPR spectroscopy.
  • Crystalline, Mixed-Valence Manganese Analogue of Prussian Blue: Magnetic, Spectroscopic, X-ray and Neutron Diffraction Studies
    P. Franz, C. Ambrus, A. Hauser, D. Chernyshov, M. Hostettler, J. Hauser, L. Keller, K. Krmer, H. Stoeckli-Evans, P. Pattison, H.-B. Brgi and S. Decurtins
    Journal of the American Chemical Society, 126 (50) (2004), p16472-16477
    DOI:10.1021/ja0465451 | unige:3247 | Abstract | Article HTML | Article PDF
 
The compound of stoichiometry Mn(II)3[Mn(III)(CN)6]2·zH2O (z = 12−16) (1) forms air-stable, transparent red crystals. Low-temperature single crystal optical spectroscopy and single crystal X-ray diffraction provide compelling evidence for N-bonded high-spin manganese(II), and C-bonded low-spin manganese(III) ions arranged in a disordered, face-centered cubic lattice analogous to that of Prussian Blue. X-ray and neutron diffraction show structured diffuse scattering indicative of partially correlated (rather than random) substitutions of [Mn(III)(CN)6] ions by (H2O)6 clusters. Magnetic susceptibility measurements and elastic neutron scattering experiments indicate a ferrimagnetic structure below the critical temperature Tc = 35.5 K.

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