Cyanide-Bridged [Co2IIMII] and [Co2IIM2II] Complexes Based on the [CoII(triphos)(CN)2] Building Block: Syntheses, Structures, Magnetic Properties, and Density Functional Theoretical Studies

plexes [Co2Mn], [Co2Fe], and [Co2Co], as well as both new tetranuclear complexes [Co2Mn2] and [Co2Ni2], exhibit antiferromagnetic coupling between metal centers. In contrast, the [Co2Ni] is characterized by ferromagnetic interTwo families of cationic cyanide-bridged complexes, namely, {[Co-(triphos)(CN)(2)](2)[M(MeOH)(4)]}(ClO4)(2) ([Co2M] M=Mn, Fe, Co, and Ni; triphos=1.1,1-tris((diphenylphosphino)-methyl)ethane) and {[Co(triphos)(CN)(2)](2)[M(MeOH)(4)](2)(ClO4)(4) ([CO2M2] M=Mn and Ni) have been prepared from reactions of [Co-II(triphos)(CN)(2)] and M(ClO4)(2)center dot 6H(2)O (M=Mn, Fe, Co, Ni) in methanol. The trinuclear comactions between the Co-II and Ni-II centers. The magnetic behavior for these complexes was investigated by DFT calculations and was found to derive from overlap patterns of the different magnetic orbitals as influenced by the angles of the cyanide bridges.