Heterometallic M<sup>II</sup>Ru<sup>III</sup><sub>2</sub> Compounds Constructed from <i>trans</i>-[Ru(Salen)(CN)<sub>2</sub>]<sup>-</sup> and <i>trans</i>-[Ru(Acac)<sub>2</sub>(CN)<sub>2</sub>]<sup>-</sup>. Synthesis, Structures, Magnetic Properties, and Density Functional Theoretical Study
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The synthesis, structures, and magnetic properties of four cyano-bridged MIIRuIII2 compounds prepared from the paramagnetic RuIII building blocks, trans-[Ru(salen)(CN)2]- 1 [H2salen = N,N‘-ethylenebis(salicylideneimine)] and trans-[Ru(acac)2(CN)2]- (Hacac = acetylacetone), are described. Compound 2, {Mn(CH3OH)4[Ru(salen)(CN)2]2}·6CH3OH·2H2O, is a trinuclear complex that exhibits antiferromagnetic coupling between MnII and RuIII centers. Compound 3, {Mn(H2O)2[Ru(salen)(CN)2]2·H2O}n, has a 2-D sheetlike structure that exhibits antiferromagnetic coupling between Mn and Ru, leading to ferrimagnetic-like behavior. Compound 4, {Ni(cyclam)[Ru(acac)2(CN)2]2}·2CH3OH·2H2O (cyclam = 1,4,8,11-tetraazacyclotetradecane), is a trinuclear complex that exhibits ferromagnetic coupling. Compound 5, {Co[Ru(acac)2(CN)2]2}n, has a 3-D diamond-like interpenetrating network that exhibits ferromagnetic ordering below 4.6 K. The density functional theory (DFT) method was used to calculate the molecular magnetic orbitals and the magnetic exchange interaction between RuIII and MII (MnII, NiII) ions.
