Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

•Design of coordination polymers based on penta- and heptacyanometallates.•New Ru and Re cyanide based heterobimetallic coordination complexes.•Hydrolysis and ox/red processes involving [Re(CN)7]3+ during crystallization.•High magnetic anisotropy of [M(cyclam)]3[Re(CN)7]2(H2O)n, M=Cu, Ni, complexes.

The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [{Mn(acacen)}2Ru(NO)(CN)5]n and two complexes composed of different cyanorhenates, [Ni(cyclam)]2[ReO(OH)(CN)4](ClO4)2(H2O)1.25 and [Cu(cyclam)]2[Re(CN)7](H2O)12, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]3[Re(CN)7]2 (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]3[Re(CN)7]2 complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN)n]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu4N)2[Ru(NO)(CN)5], soluble in organic media.

Graphical abstractThe very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented.Figure optionsDownload full-size imageDownload as PowerPoint slide