Syntheses, crystal structures and magnetic properties of three cyano-bridged trinuclear clusters based on modified hexacyanometalates building blocks

Three new cyano-bridged trinuclear clusters, [{Mn(phen)2}{Cr(phen)(CN)4}2]·9H2O (1), [{Ni(teta)}{Cr(phen)(CN)4}2]·2CH3OH (2) and [{Ni(teta)}{Fe(phen)(CN)4}2]·4CH3OH (3) (teta = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) have been synthesized by using [M(phen)(CN)4]− (M = CrIII, FeIII) as building blocks. Complex 1 consists of V-shaped trinuclear units (CrIII–CN–MnII–NC–CrIII), which further extend into 3-D supermolecular network via the intermolecular π–π interaction. In contrast to 1, complexes 2 and 3 are isostructural with almost linear trinuclear units (M–CN–NiII–NC–M) (M = CrIII, FeIII). The magnetic investigation reveals the presence of intracluster antiferromagnetic coupling for complex 1 and intramolecular ferromagnetic coupling for complexes 2 and 3.