Luminescent and Sublimable Binaphthyl-Based Field-Induced Lanthanide Single-Molecule Magnets

Abstract

The association of the [Ln(hfac)3(H2O)2] metallic building blocks with the new ligand [1,1’-binaphthalene]-8,8’-diylbis(diphenylphosphine oxide) (L) led to the formation of three mononuclear complexes of formula [Ln(hfac)3(L)] (LnIII = Eu (1), Dy (2) and Yb (3)). The mononuclear character of the compounds is due to the bidentate coordination mode adopted by L to link the metal. L allows the observation of the characteristic visible 5D0  7FJ (J = 0-4) EuIII- and near infrared 2F5/2  2F7/2 YbIII- emissions while 2 is only weakly emissive due to the mismatch between the energy positions of the triplet excited state of the ligand and DyIII emissive state. The magnetic data reveal a field-induced Single-Molecule Magnet (SMM) behavior for 2 and 3 with an efficient suppression of the Quantum Tunneling of the Magnetization (QTM). The slow magnetic relaxation occurs through a Raman process while the Orbach contribution is discarded as confirmed by the correlation with the MJ states energy splitting provided by the luminescence spectrum of 3.