Synthesis, Crystal Structures, and Magnetic Properties of Heterodimetallic Ru III –3d Coordination Compounds Based on a Meridional Tricyanoruthenium(III) Building Block

Abstract

The synthesis, crystal structures, and magnetic properties of three cyano-bridged heterodimetallic compounds prepared from the paramagnetic RuIII building block mer-[RuIII(CN-sap)(CN)3]2– (1) are described. Complex 1 reacts with [MnII(LN5)(Cl)(H2O)]Cl and [MnII(bipy)2(Cl)2] (bipy = bipyridine) to produce the 1D zigzag chain {[RuIII(CN-sap)(CN)](μ-CN)2[MnII(LN5)]·3MeOH}n {2; LN5 = 2,13-dimethyl-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene, CN-sapH2 = 2-hydroxy-N-(2-hydroxyphenyl)benzimidoyl cyanide} and the octanuclear compound {[RuIII(CN-sap)(CN)](μ-CN)2[MnII(bipy)(MeOH)][RuIII(CN-sap)](μ-CN)3[MnII(bipy)2]}2·8MeOH (3), respectively. The MnII centers have a pentagonal-bipyramidal environment in 2 and a distorted octahedral environment in 3. Complex 1 reacts with [NiII(cyclen)(Cl)2] (cyclen = 1,4,7,10-tetraazacyclododecane) in MeOH to produce the molecular square {[RuIII(CN-sap)(CN)](μ-CN)2[NiII(cyclen)]}2·8MeOH (4). Compounds 2 and 3 exhibit antiferromagnetic coupling between the RuIII and MnII centers, whereas 4 exhibits ferromagnetic coupling between the RuIII and NiII centers through the cyano bridges.