The role of ligands in controlling the electronic structure and magnetic properties of Mn4 single-molecule magnets

We present our studies of electronic structure and magnetic properties of Mn4+Mn33+ single-molecule magnets (SMM), i.e, [Mn4+Mn33+O3Cl4(OAc)3(py)3] (py = pyridine) and [Mn4+Mn33+O3Cl(OAc)3(dbm)3] (dbmH = dibenzoyl-methane) molecules by using a first-principles all-electron relativistic method within spin-polarized density functional theory. To investigate the possibility of ligands controlling the electronic structure and magnetic properties, we designed and calculated the geometric and electronic structures of twelve other Mn4+Mn3n+ (n = 2, 3, 4) molecules with different peripheral-ligand configurations. The electronic structure of Mnn+ ions, and the interatomic distances, electronic structure and magnetic properties of Mn4+Mn3n+ molecules display an interesting variation with n.