Structures And Properties Of Complexes Based On [Mn~Ⅲ(SB)]~+ Bridged By Cyanide

In this work, based on seven coordination-acceptor building blocks [Mn（SB）]⁺ and polycyanometallate as building units, twelve polynuclear complexes have been obtained. All the complexes were characterized by X-ray single crystal diffraction, some of these complexes were characterized by magnetic susceptibility. The specific contents are shown as follows:Four complexes have been synthesized by using [Fe（CN）₆]^3- as building block. The structural analyses show that complex 1 consists of one-dimensional alternating chains formed by the [Fe（CN）₆]^3- and [Mn（SB）]⁺. The adjacent chains are then connected via the K⁺ to give the two-dimensional networ structure. Complex 2 consists of 1D alternating chains formed by the FeMn₂ and K⁺. The magnetic analysis indicates that the cyanogen bridging ligand propagates strong ferromagnetic exchange. Complex 3 formed by the {[Mn（rac-3-MeOsalcy）（CH₃OH）][Fe（CN）₆]}2- binuclear anions and（[Mn（rac-3-MeOsalcy）（CH₃OH）（ H₂O）]⁺ and K⁺） cations. In ion-pair complex 4, a very weak antiferromagnetic exchange between paramagnetic units.Four complexes have been synthesized by using [Cr（CN）₆]^3- or [Cr（CN）₅（NO）]3-as building block. In ion-pair complex 5, [Cr（CN）₆]^3-、[K（18-Cr-6）（H₂O）]⁺ and [Mn（5-Cl-salen）（H₂O）₂]⁺ existed freely in crystal. Complex 6 formed by the CrIIIMn binuclear anions and（ [Mn（rac-3-Me Osalcy）（H₂O）₂]⁺ and K⁺） cations.The same to complex 6, complex 7 formed by the CrIMn binuclear anions and（[Mn（R,R-3-MeOsalcy）（H₂O）₂]⁺ and K⁺）.Five complexes have been synthesized by using [Au（CN）₂]- or [N（CN）₂]-.Dicyanoaurate（I） anion acts as monodentate ligand to form the binuclear complex 8. Adjacent binuclear units formed tetranuclear part by hydrogen bonds. The weakly bonding interactions between gold（I） centres linked repeating tetranuclear units forming an alternating neutral chain. Complex 9 have the polymer structure in which the dicyanamide anion binds the paramagnetic Mn（III） complexes with the Schiff bases into one-dimensional chains. Unlike them, in complex 10、11、12 the monomer units containing water and the dicyanamide anion as terminal ligands form dimers due to hydrogen bonds. The study of the magnetic properties of complex 9 shows a weak antiferromagnetic interaction between the Mn（III） ions through the dicyanamide bridges in these complexes. The applied magnetic field for complex 9 shows a spin-flop transition at 2.0 T. Magnetic studies reveal that in complex 12 there are antiferromagnetic interaction between binuclear units.