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 Mn 4 + Mn 3 3 + single-molecule magnets (SMM), i.e, [ Mn 4 + Mn 3 3 + O 3 Cl 4 ( OAc ) 3 ( py ) 3 ] (py = pyridine) and [ Mn 4 + Mn 3 3 + O 3 Cl ( 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 Mn 4 + Mn 3 n + (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 Mn 4 + Mn 3 n + molecules display an interesting variation with n.