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Stabilization of Ni2+ dimers in Prussian Blue derivatives built up from hexacyano Mo6 cluster based compounds: experimental and theoretical investigations of magnetic properties

Abstract

Two new octahedral molybdenum cyanide cluster compounds, namely [{Ni(NH3)6}4{Ni2(NH3)8}1][Mo6Br6Q2(CN)6]3.12H2O, Q = S(1) and Se (2) have been synthetized as single crystals by slow diffusion of a solution of nickel chloride into aqueous ammonia solutions of K2Cs2[Mo6Br6Q2(CN)6] molybdenum cyanide cluster-based compound. Both 1 and 2 were structurally characterized by single-crystal X-ray diffraction. They are isostructural and crystallize in the cubic system (Im-3m (n° 229); Z = 2, a = 18.147(1) Å, V = 5976(1) Å3; and a = 18.188(2) Å, V = 6016(2) Å3; for 1 and 2, respectively). 1 and 2 are based on the association of [Mo6Bri6Qi2(CN)a6]4- (Q = S, Se) cluster anions with Ni2+ dimer-based cubic [Ni2(NH3)8]4+ and octahedral [Ni(NH3)6]2+ cations. The structure is based on 2-fold interpenetrated [{Ni(NH3)6}4{Ni2(NH3)8}1][Mo6Br6Q2(CN)6]3.12H2O frameworks related one to each other by [½, ½, ½] translation. The unit cell is based on a body-centered cubic framework of cubic [Ni2(NH3)8]4+. The [Mo6Bri6Qi2(CN)a6]4- (Q = S, Se) cluster units are located in the middle of the edges and in the center of the faces of the cell. The [{Ni(NH3)6}]2+ cations are located at the center of the cubes of a/2 edge. The Ni2+ dimers [Ni2(NH3)8]4+ are stabilized by hydrogen bonds between cyanide ligands of the cluster unit and hydrogen atoms of ammonia molecules. Both compounds exhibit a weak antiferromagnetic coupling within the [Ni2(NH3)8]4+ dimer entities at low temperature together with a paramagnetic behavior originating from the octahedral [{Ni(NH3)6}]2+ complexes cations.

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Publication details

The article was received on 27 Jul 2017, accepted on 05 Dec 2017 and first published on 06 Dec 2017


Article type: Paper
DOI: 10.1039/C7DT02748F
Citation: Dalton Trans., 2017, Accepted Manuscript
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    Stabilization of Ni2+ dimers in Prussian Blue derivatives built up from hexacyano Mo6 cluster based compounds: experimental and theoretical investigations of magnetic properties

    G. Daigre, K. Costuas, M. Tarasenko, A. Yu. Ledneva, N. naumov, P. Lemoine, T. Guizouarn, Y. Molard, M. Amela-Cortes, N. Audebrand and S. Cordier, Dalton Trans., 2017, Accepted Manuscript , DOI: 10.1039/C7DT02748F

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