Photoluminescent Lanthanide(III) Coordination Polymers with Bis(1,2,4-Triazol-1-yl)Methane Linker

Abstract

A series of new lanthanide(III) coordination polymers with the general formula [Ln(btrm)2(NO3)3]n, where btrm = bis(1,2,4-triazol-1-yl)methane and Ln = Eu3+, Tb3+, Sm3+, Dy3+, Gd3+ were synthesized and characterized by IR-spectroscopy, elemental, thermogravimetric, single-crystal, and powder X-ray diffraction analyses. Europium(III), samarium(III), terbium(III), and gadolinium(III) coordination polymers demonstrate thermal stability up to 250 °C, while dysprosium(III) is stable up to 275 °C. According to single-crystal X-ray diffraction analysis, the ligand exhibits a bidentate-bridging coordination mode, forming a polymeric chain of octagonal metallocycles. The photoluminescence of the free ligand in the polycrystalline state is observed in the ultraviolet range with a quantum yield of 13%. The energy transfer from the ligand to the lanthanide ions was not observed for all obtained coordination polymers. However, there are sharp bands of lanthanide(III) ions in the diffuse reflectance and excitation spectra of the obtained compounds. Therefore, Ln(III) luminescence arises, most probably, from the enhancement of f-f transition intensity under the influence of the ligand field and non-centrosymmetric interactions.