The synthesis, structures, and magnetic properties of four cyano-bridged M(II)Ru(III)2 compounds prepared from the paramagnetic Ru(III) 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 Mn(II) and Ru(III) 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 Ru(III) and M(II) (Mn(II), Ni(II)) ions.

A novel dicyanoosmium(III) complex, trans-Ph(4)P[Os(III)(salen)(CN)(2)].CH(2)Cl(2).H(2)O (1; Ph(4)P(+) = tetraphenylphosphonium cation, salen(2-) = N,N'-ethylenebis(salicylideneaminato) dianion), has been synthesized and structurally characterized. Reactions of 1 with [Cu(Me(3)tacn)(H(2)O)(2)](ClO(4))(2) (Me(3)tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) under different conditions produce the 1-D ferromagnetic zigzag chains [Os(salen)(CN)(2)](2)[Cu(Me(3)tacn)].CH(3)OH (2) and [Os(salen)(CN)(2)][Cu(Me(3)tacn)].ClO(4) (3).