Effect of the Composition of Lanthanide Complexes on Their Luminescence Enhancement by Ag@SiO₂ Core-Shell Nanoparticles.

Metal-enhanced luminescence of lanthanide complexes by noble metal nanoparticles has attracted much attention because of its high efficiency in improving the luminescent properties of lanthanide ions. Herein, nine kinds of europium and terbium complexes-RE(TPTZ)(ampca)₃·3H₂O, RE(TPTZ)(BA)₃·3H₂O, RE(phen)(ampca)₃·3H₂O, RE(phen)(PTA)·3H₂O (RE = Eu, Tb) and Eu(phen)(BA)₃·3H₂O (TPTZ = 2,4,6-tri(2-pyridyl)-s-triazine, ampca = 3-aminopyrazine-2-carboxylic acid, BA = benzoic acid, phen = 1,10-phenanthroline, PTA = phthalic acid)-have been synthesized. Meanwhile, seven kinds of core-shell Ag@SiO₂ nanoparticles of two different core sizes (80-100 nm and 40-60 nm) and varied shell thicknesses (5, 12, 20, 30 and 40 nm) have been prepared. The combination of these nine types of lanthanide complexes and seven kinds of Ag@SiO₂ nanoparticles provides an opportunity for a thorough investigation of the metal-enhanced luminescence effect. Luminescence spectra analysis showed that the luminescence enhancement factor not only depends on the size of the Ag@SiO₂ nanoparticles, but also strongly relates to the composition of the lanthanide complexes. Terbium complexes typically possess higher enhancement factors than their corresponding europium complexes with the same ligands, which may result from better spectral overlap between the emission bands of Tb complexes and surface plasmon resonance (SPR) absorption bands of Ag@SiO₂. For the complexes with the same lanthanide ion but varied ligands, the complexes with high enhancement factors are typically those with excitation wavelengths located nearby the SPR absorption bands of Ag@SiO₂ nanoparticles. These findings suggest a combinatorial chemistry strategy is necessary to obtain an optimal metal-enhanced luminescence effect for lanthanide complexes.