2013-05-26 10:19:03 637 Claude Daul, Cédrick Rauzy, Silvio Decurtins, Patrick Franz, Andreas Hauser Daul, Claude Rauzy, Cédrick Decurtins, Silvio Franz, Patrick Hauser, Andreas International Journal of Quantum Chemistry Intl. J. Quantum Chem. 0020-7608 2005 101 6 753 760 H cluster; cyanide bridging ligand; DFT; manganese complexes; Prussian blue analogue cluster cyanide bridging ligand DFT manganese complexes Prussian blue analogue http://www3.interscience.wiley.com/cgi-bin/abstract/109746160/ABSTRACT http://www3.interscience.wiley.com/cgi-bin/fulltext/109746160/HTMLSTART http://www3.interscience.wiley.com/cgi-bin/fulltext/109746160/PDFSTART The cubic Prussian blue analogue Mn₃[Mn(CN)₆]₂ · 15 H₂O, which has the advantage of being transparent and magnetic (T_N = 35 K) at the same time, has been investigated by density functional theory (DFT) calculations. The three-dimensional structure is built of Mn^II ions linked to Mn^III 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 ³T₁ → ¹T₂ transition, which has been observed by single-crystal near-IR spectra of Mn₃[Mn(CN)₆]₂ · 15 H₂O.

]]> H164I328P132 10.1002/qua.20333 3620 http://www.unige.ch/sciences/chifi/publis/pics/double/ref00637.png http://www.unige.ch/sciences/chifi/publis/refs_pdf/ref00637.pdf 638 Patrick Franz, Christina Ambrus, Andreas Hauser, Dmitry Chernyshov, Marc Hostettler, Jürg Hauser, Lukas Keller, Karl Krämer, Helen Stoeckli-Evans, Philip Pattison, Hans-Beat Bürgi, and Silvio Decurtins Franz, Patrick Ambrus, Christina Hauser, Andreas Chernyshov, Dmitry Hostettler, Marc Hauser, Jürg Keller, Lukas Krämer, Karl Stoeckli-Evans, Helen Pattison, Philip Bürgi, Hans-Beat Decurtins, Silvio Journal of the American Chemical Society J. Am. Chem. Soc. 0002-7863 2004 126 50 16472 16477 H http://pubs.acs.org/cgi-bin/abstract.cgi/jacsat/2004/126/i50/abs/ja0465451.html http://pubs.acs.org/cgi-bin/article.cgi/jacsat/2004/126/i50/html/ja0465451.html http://pubs.acs.org/cgi-bin/article.cgi/jacsat/2004/126/i50/pdf/ja0465451.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 T_c = 35.5 K.

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