Perfluoroalkyl Chain Length Effect on Crystal Packing and [LnO8] Coordination Geometry in Lanthanide-Lithium β-Diketonates: Luminescence and Single-Ion Magnet Behavior

Abstract

Functionalized perfluoroalkyl lithium β-diketonates (LiL) react with lanthanide(III) salts (Ln = Eu, Gd, Tb, Dy) in methanol to give heterobimetallic Ln-Li complexes of general formula [(LnL₃)(LiL)(MeOH)]. The length of fluoroalkyl substituent in ligand was found to affect the crystal packing of complexes. Photoluminescent and magnetic properties of heterobimetallic β-diketonates in the solid state are reported. The effect of the geometry of the [LnO₈] coordination environment of heterometallic β-diketonates on the luminescent properties (quantum yields, phosphorescence lifetimes for Eu, Tb, Dy complexes) and single-ion magnet behavior (U_eff for Dy complexes) is revealed.

Keywords: crystal packing; lanthanide; luminescence; single-ion magnet; β-diketonates.