Synthesis and luminescent properties of lanthanide homoleptic mercaptothi(ox)azolate complexes: Molecular structure of Ln(mbt)3 (Ln = Eu, Er)

The thiolate complexes of rare earth metals Ln(SR)3 (La, HSR = 2-mercaptothiazoline (1); La, HSR = 2-mercaptobenzoxazole (2); Y, La, Sm, Eu, Tb, Gd, Er, Tm, HSR = 2-mercaptobenzothiazole (3)) were synthesized in 84–97% yield by the reactions of silylamides Ln[N(SiMe3)2]3 with respective thiols. The products were characterized by elemental analysis, IR and UV/Vis spectroscopy. The structures of 3(Eu) and 3(Er) were determined by single-crystal X-ray diffraction. All obtained compounds revealed efficient luminescence in the region 400–550 nm at 293 K assigned to the ligands emission. Besides, the luminescent spectra of thiolates 3 at 77 K displayed the phosphorescent band of the ligand at 550 nm and in the cases of 3(Eu) and 3(Tb) the sets of emissions bands characteristic for Eu3+ and Tb3+ ions.

Graphical abstractThe thiolate complexes of rare earth metals Ln(SR)3 (La, HSR = 2-mercaptothiazoline (1); La, HSR = 2-mercaptobenzoxazole (2); Y, La, Sm, Eu, Tb, Gd, Er, Tm, HSR = 2-mercaptobenzothiazole (3)) were synthesized by the reactions of silylamides Ln[N(SiMe3)2]3 with respective thiol. Their photoluminescent properties were studied.Figure optionsDownload full-size imageDownload as PowerPoint slide