Tuning the optical and magnetic properties of lanthanide single-ion magnets using nitro-functionalized trispyrazolylborate ligands

Abstract

We report the synthesis, crystal structures, photophysical and magnetic properties of 11 novel lanthanide complexes with the asymmetrically functionalized trispyrazolylborate ligand 4-nitrotrispyrazolylborate, 4-NO₂Tp^-: [Ln(4-NO₂Tp)₃] (Ln = La-Dy, except Pm). In-depth photophysical characterization of the ligands via luminescence, reflectance and absorption spectroscopic techniques, decay lifetimes, quantum yields supported by time-dependent density functional theory (TD-DFT) and natural bond order (NBO) analysis reveal that n-NO₂Tp^- ligands are dominated by intra-ligand charge transfer (ILCT) transitions and that second-sphere interactions are critical to the stabilization of the T₁ state of n-NO₂Tp^- ligands and hence their ability to sensitize Ln³⁺ emission. The luminescence properties of the complexes indicate that 4-NO₂Tp^- is a poor sensitizer of Ln³⁺ emission, unlike 3-NO₂Tp^-. Moreover, [Nd(4-NO₂Tp)₃] (crystallized as a hexane solvate) displays single-molecule magnet (SMM) properties, with longer relaxation times and larger barrier than the non-functionalized [NdTp₃], attributed to the addition of the NO₂-group and subsequent rigidification of the molecular structure.