3D-Frameworks and 2D-networks of lanthanide coordination polymers with 3-pyridylpyrazole: photophysical and magnetic properties

Abstract

A series of 15 lanthanide-containing coordination polymers, both 3D- and 2D-networks, as well as complexes of Ln-trichlorides with 3-(3-pyridyl)pyrazole (3-PyPzH), were synthesized. A large structural diversity is observed depending on the ligand content: 3∞[Ln(3-PyPzH)Cl₃], Ln = Eu and Gd, of sra topology, 2∞[Sm(3-PyPzH)Cl₃], 2∞[Ln₂(3-PyPzH)₃Cl₆]·2solv, Ln = Eu³⁺, Tb³⁺, Dy³⁺, Ho³⁺ and Er³⁺, solv = Tol and MeCN, of sql topology and 2∞[Ln(3-PyPzH₂)Cl₄], Ln = La and Nd, of hcb topology with salt like complexes of the formula [(3-PyPzH₂)][Ln(3-PyPzH)₂Cl₄], Ln = Eu, Tb, Dy and Ho. The products were characterized by single-crystal and powder X-ray diffraction, high-temperature X-ray diffraction, differential thermal analysis and thermogravimetry (DTA/TG) combined with mass spectrometry, differential scanning calorimetry (DSC), IR-spectroscopy, UV-visible spectrophotometry, photoluminescence spectroscopy, and magnetic susceptibility. Absorption spectroscopy shows ion-specific 4f-4f transitions that can be assigned to Sm³⁺, Eu³⁺, Dy³⁺, Ho³⁺ and Er³⁺ in a wide range from the UV-VIS to NIR region. An excellent antenna effect through ligand-metal energy transfer was observed in 2∞[Tb₂(3-PyPzH)₃Cl₆]·2solv, leading to high efficiency of the luminescence indicated by a quantum yield up to 76%. Direct current magnetic susceptibility studies reveal the absence of interatomic interaction for Dy³⁺ and Er³⁺ and weak ferromagnetic interaction for Ho³⁺. Thermal analysis shows good stability up to 365 °C for 2∞[Ho₂(3-PyPzH)₃Cl₆]·2MeCN.