Structural Diversity of Lanthanide 3-Nitrotrispyrazolylborates: Tunable Nuclearity and Intra-Ligand Charge Transfer Sensitization of Visible and NIR Ln3+ Emission

Abstract

Reported are the syntheses, crystal structures, and photophysical properties of 28, novel lanthanide compounds across five structural types, [Ln(3-NO₂Tp)₂(NO₃)] (1-Ln, Ln = La-Tm, except Pm), [Bu₄N][Ln(3-NO₂Tp)(NO₃)₃] (2-Ln, Ln = Yb, Lu), [Eu(3-NO₂Tp)₂Cl(H₂O)]·2ⁱPrOH (3-Eu), [{Ln(3-NO₂Tp)₂}₂(μ₂-CO₃)]·MeOH (4-Ln, Ln = La-Gd, except Pm), and [{Ln(3-NO₂Tp)}₄(μ₂-OMe)₆(μ₄-O)] (5-Ln, Ln = Pr-Tb, except Pm) with the 3-nitrotrispyrazolylborate (3-NO₂Tp^-) ligand. The reaction of methanol or isopropanol solutions of LnX₃ (X = Cl, NO₃) with the tetrabutyl ammonium salt of the flexidentate 3-NO₂Tp^- ([Bu₄N][3-NO₂Tp]) yields Ln(3-NO₂Tp)_x complexes of various nuclearities as either monomers (1-Ln, 2-Ln, 3-Eu), dimers (4-Ln), or tetramers (5-Ln) owing to the efficient conversion of atmospheric CO₂ to CO₃^2- (dimers) or ligand controlled solvolysis of lanthanide ions (tetramers). 3-NO₂Tp^- is an efficient sensitizer for both the visible and near-IR (NIR) emissions of most of the lanthanide series, except thulium. Optical measurements, supported by density functional theory calculations, indicate that the dual visible and NIR Ln³⁺ emission arises from two intraligand charge transfer (ILCT) transitions of 3-NO₂Tp^-. This is the first report of lanthanide complexes with a nitro-functionalized pyrazolylborate ligand. The derivatization of the known Tp^- ligand results in new coordination chemistry governed by the increased denticity of 3-NO₂Tp^-, imparting remarkable structural diversity and charge transfer properties to resultant lanthanide complexes.