Photophysical Properties of Lanthanide Hybrids Covalently Bonded To Functionalized MCM-41 by Modified Aromatic Carboxylic Acids

Abstract

MCM-41 mesoporous silica has been functionalized with aromatic carboxylic acids salicylic acid (Sal) and 2-hydroxyl-3-methylbenzoic acid (HMBA) through co-condensation approach of tetraethoxysilane (TEOS) in the presence of the cetyltrimethylammonium bromide (CTAB) surfactant as a template. Organic ligands salicylic acid or 2-hydroxyl-3-methylbenzoic acid grafted to the coupling agent 3-(triethoxysilyl)-propyl isocyanate (TEPIC) was used as the precursor for the preparation of an organic-inorganic hybrid materials. Novel organic-inorganic mesoporous luminescent hybrid containing Ln(3+) (Tb(3+), Eu(3+)) complexes covalently attached to the functionalized ordered mesoporous MCM-41, which were designated as Ln-Sal-MCM-41 and Ln-HMBA-MCM-41, respectively, were obtained by sol-gel process. The luminescence properties of these resulting materials were characterized in detail, and the results reveal that luminescent mesoporous materials have high surface area, uniformity in the mesopore structure and good crystallinity. Moreover, the mesoporous material covalently bonded Tb(3+) complex (Tb-Sal-MCM-41 and Tb-HMBA-MCM-41) exhibit the stronger characteristic emission of Tb(3+) and longer lifetime than the corresponding Eu-containing materials Eu-Sal-MCM-41 and Eu-HMBA-MCM-41 due to the triplet state energy of modified organic ligands Sal-TEPIC and HMBA-TEPIC match with the emissive energy level of Tb(3+) very well. In addition, the luminescence lifetime and emission quantum efficiency of (5)D(0) Eu(3+) excited state also indicates the efficient intramolecular energy transfer process in Tb-SAL-MCM-41 and Tb-HMBA-MCM-41.