Tuning the luminescence properties of lanthanide coordination polymers with Ag@SiO2 nanoparticles

Abstract

A series of core–shell Ag@SiO₂ nanoparticles with different core diameters and shell thicknesses have been prepared by a modified-Stöber method. They provide a facile route to tune the luminescence intensities, lifetimes and quantum efficiencies of lanthanide coordination polymers in the solid powder state. The coordination polymers [Tb₂(p-PTA)₃(H₂O)₂]_n, [Tb₂(o-PTA)₃(H₂O)₂]_n, [Eu₂(p-PTA)₃(H₂O)₂]_n and [Eu₂(o-PTA)₃(H₂O)₂]_n (PTA = phthalic acid) are synthesized and subsequently bound to the surface of Ag@SiO₂ nanoparticles. The luminescence intensities of the lanthanide complexes are enhanced as high as 10.8 times. The enhancement times depend on the core diameter and shell thickness of the Ag@SiO₂ nanoparticles. Importantly, by simply controlling the ratios between the complexes and the nanoparticles, the luminescence intensities, lifetimes and quantum efficiencies of the lanthanide complexes can be tuned in wide ranges. Typically, the luminescence lifetime of [Eu₂(p-PTA)₃(H₂O)₂]_n powder increases from 451 μs to 783 μs when 300 μL Ag@SiO₂ solution is added. Meanwhile, the luminescence quantum efficiency of the complex increases from 32.1% to 40.9%. The change of the luminescence properties of the lanthanide coordination polymers can be ascribed to the surface plasmon resonance effect of the Ag@SiO₂ nanoparticles as well as the decrease of the nonradiative decay rates of the complexes.