Highly luminescent tris(beta-diketonate)europium(III) complexes immobilized in a functionalized mesoporous silica
authors Gago, S; Fernandes, JA; Rainho, JP; Ferreira, RAS; Pillinger, M; Valente, AA; Santos, TM; Carlos, LD; Ribeiro-Claro, PJA; Goncalves, IS
nationality International
journal CHEMISTRY OF MATERIALS
keywords BETA-DIKETONATE COMPLEXES; MCM-41 MOLECULAR-SIEVES; RARE-EARTH COMPLEX; CURVED-WAVE THEORY; ENERGY-TRANSFER; LANTHANIDE COMPLEXES; HETEROCYCLIC AMINES; EXAFS CALCULATIONS; EMISSION-SPECTRUM; THIN-FILMS
abstract The mesoporous silica MCM-41 functionalized with a chelating pyrazolylpyridine ligand (MCM-41-L2) was used as a support for the immobilization of tris(beta-diketonate) complexes Ln(NTA)(3) [Ln = Eu, Gd; NTA = 1-(2-naphthoyl)-3,3,3-trifluoroacetonate]. The derivatized materials were characterized by powder X-ray diffraction, N-2 adsorption, FTIR and IT Raman spectroscopy, Eu L-3-edge X-ray absorption fine structure (XAFS), diffuse reflectance, and photoluminescence spectroscopy. The spectroscopic studies, supported by ab initio calculations, provide strong evidence that the immobilized europium(III) complex is 8-coordinate, with a local coordination environment that is similar to that for a model complex containing the ligand ethyl[3-(2-pyridyl)-1-pyrazolyl] acetate (L1). No emission from the pyrazolylpyridine ligands is observed in the room-temperature emission spectrum of MCM-41-L2/Eu, despite the fact that only about one-third are engaged in coordination with Eu3+ ions. In contrast, the pyrazolylpyridine groups in the precursor ligand-silica exhibit efficient emission. Furthermore, the radiance value measured for MCM-41-L2/Eu (0.33 mu W cm(-2)) is only about one-half of that measured for the complex Eu(NTA)(3)center dot L1 (0.73 mu W cm(-2)), even though the concentration of emitting centers in the MCM material is much lower. The results point to the existence of an unusual two-step intermolecular energy transfer between "free" and complexed ligands in MCM-41-L2/Eu, culminating in the observation of enhanced Eu3+ luminescence.
publisher AMER CHEMICAL SOC
issn 0897-4756
year published 2005
volume 17
issue 20
beginning page 5077
ending page 5084
digital object identifier (doi) 10.1021/cm0514490
web of science category Chemistry, Physical; Materials Science, Multidisciplinary
subject category Chemistry; Materials Science
unique article identifier WOS:000232326700025

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