Variable Luminescence and Chromaticity of Homoleptic Frameworks of the Lanthanides together with Pyridylpyrazolates

Abstract

Homoleptic, 3D coordination polymers of the formula ³³ _∞ [Ln(3-PyPz)₃ ] and ³ _∞ [Ln(4-PyPz)₃ ], (3-PyPz)^- =3-(3-pyridyl)pyrazolate anion, (4-PyPz)^- =3-(4-pyridyl)pyrazolate anion, both C₈ H₆ N₃ ^- , Ln=Sm, Eu, Gd, Tb, Dy, were obtained as highly luminescent frameworks by reaction of the lanthanide metals (Ln) with the aromatic heterocyclic amine ligands 3-PyPzH and 4-PyPzH. The compounds form two isotypic series of 3D coordination polymers and exhibit fair thermal stability up to 360 °C. The luminescence properties of all ten compounds were determined in the solid state, with an antenna effect through ligand-metal energy transfer leading to high efficiency of the luminescence displayed by good quantum yields of up to 74 %. The emission is mainly based on ion-specific lanthanide-dependent intra 4 f-4 f transitions for Tb³⁺ : green, Dy³⁺ : yellow, Sm³⁺ : orange-red, Eu³⁺ : red. For the Gd³⁺ -containing compounds, the yellow emission of ligand triplet-based phosphorescence is observed at room temperature and 77 K. Co doping of the Gd-containing frameworks with Eu³⁺ and Tb³⁺ allow further shifting of the chromaticity towards white light emission.

Keywords: N ligands; coordination polymers; homoleptic; lanthanides; luminescence.