Heterometallic 3d–4d coordination polymers assembled from trans -[Ru III (L)(CN) 2 ] − tectons and 3d cations

International audienceFive new cyanido-bridged heterometallic coordination polymers have been obtained by reacting PPh4[RuIII(salpn)(CN)2]·H2O (1) and AsPh4[RuIII(valen)(CN)2]·8.5H2O (2) (H2salpn and H2valen being Schiffbase proligands resulting from the condensation reaction of salicylaldehyde with 1,3-propanediamine and, respectively, o-vanillin with 1,2-ethanediamine) with divalent transition metal perchlorate salts: 1 1 [{RuIII(salpn)(CN)2}3{MII(DMF)3}2](ClO4)·4DMF (MII = Mn, 3; Co, 4) and 12 [{RuIII(valen)(CN)2}4{MII(DMF)3}2 {MII(DMF)4}](ClO4)2·4DMF (MII = Mn, 5; Co, 6; Ni, 7), respectively. The dicyanido species, trans-[Ru(salpn) (CN)2]− and trans-[Ru(valen)(CN)2]−, act as metalloligands with the 3d metal ions. Compounds 3 and 4 are isostructural one-dimensional (1D) coordination polymers with a ladder topology. Each MII ion is hexacoordinatedby three cyanido groups arising from three {Ru(salpn)(CN)2} units and by the oxygen atoms from three DMF molecules, which are coordinated at meridional positions. Compounds 5–7 are also isostructural, their structures consisting of 2D networks with a herringbone topology. The magnetic susceptibility measurements of these 1D and 2D systems reveal the presence of dominating RuIII–MII antiferromagnetic (AF) interactions in compounds 3, 4, 5 and 6, while ferromagnetic RuIII–NiII interactions are observed in 7. All these compounds stay in their paramagnetic state down to 1.8 K except compound 4 which possesses a 3D ordered AF ground state