Role of Dicarboxylate Linkers in MnIII-Salicylaldoximate Based Extended Structures: Synthesis, Structures, and Magnetic Behavior

Abstract

Four new oxo-centered Mn(III)-salicylaldoximate triangle-based extended complexes [Mn(III)6O2(salox)6(EtOH)4(phda)]n·(saloxH2)n·(2H2O)n (1), [Mn(III)6O2(salox)6(MeOH)5(5-I-isoph)]n·(3MeOH)n (2), [Mn(III)6O2(salox)6(MeOH)4(H2O) (5-N3-isoph)]n·(4MeOH)n (3) and [Mn(III)3NaO(salox)3(MeOH)4(5-NO2-isoph)]n·(MeOH)n (H2O)n (4) [salox=salicylaldoximate, phda=1,3-phenylenediacetate, isoph=isophthalate] have been synthesized under similar reaction conditions. Single crystal X-ray structures show that in 1, only one type of Mn6 cluster is arranged in 1D, whereas in 2 and 3 there are two types of clusters, differing in the way the triangle units are joined and assembled. In complex 4, however, the basic building structure is heteronuclear and based on Mn3 units extended in 2D. Susceptibility measurements (dc and ac) over a wide range of temperatures and fields show that the complexes 1, 2, and 3 behave as single molecule magnets (SMMs) with S=4 ground state, while 4 is dominantly antiferromagnetic with a ground spin state S=2. Density functional theory calculations have been performed on model complexes to provide a qualitative theoretical interpretation for their overall magnetic behavior.