The cubic Prussian blue analogue Mn3[Mn(CN)6]2 · 15 H2O, which has the advantage of being transparent and magnetic (TN = 35 K) at the same time, has been investigated by density functional theory (DFT) calculations. The three-dimensional structure is built of MnII ions linked to MnIII ions by μ-bridging cyanides, to form a crystal structure, which is related to the NaCl type. In a first step, the relative stabilities of the mononuclear complexes [Mn(CN)6]z- (z = 2 to 4) have been studied as a function of the oxidation state, spin configuration, and the linkage isomerism of the cyanide ligand. The results we have obtained by this investigation are in good agreement with our chemical expertise. In addition, the calculations have been extended to the dinuclear [Mn2(CN)11]z- (z = 5 and 6) clusters. Furthermore, we used DFT to model the magnetic properties as well as the 3T11T2 transition, which has been observed by single-crystal near-IR spectra of Mn3[Mn(CN)6]2 · 15 H2O.
  
  • 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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