MCM-41 derivatised with pyridyl groups and its use as a support for luminescent europium(III) complexes

authors	Bruno, SM; Coelho, AC; Ferreira, RAS; Carlos, LD; Pillinger, M; Valente, AA; Ribeiro-Claro, P; Goncalves, IS
nationality	International
journal	EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
author keywords	mesoporous materials; lanthanides; luminescence; pyridine; beta-diketone
keywords	MESOPOROUS MCM-41; MOLECULAR-SIEVES; METAL-COMPLEXES; SILICA; LIGANDS; 1,10-PHENANTHROLINE; CHEMISTRY; CATALYSTS; ADDUCTS; SBA-15
abstract	An organic-inorganic hybrid ligand silica was prepared by reaction of the ordered mesoporous silica MCM-41 with 3-triethoxysilylpropyl 4-pyridylacetamide. Elemental analysis indicated that a pyridyl group loading of 0.93 mmolg(-1) was achieved. The derivatised material was further characterised by powder X-ray diffraction, N(2) adsorption, thermogravimetric analysis, FTIR and Raman spectroscopy, and (13)C and (29)Si CP MAS NMR spectroscopy. Pyridyl-functionalised MCM-41 (L '') was treated with chloroform solutions of lanthanide tris-beta-diketonate complexes Ln(nta)(3)(H(2)O)(2) [Ln = Eu, Gd; nta = 1-(2-naphthoyl)-3,3,3-trifluoroacetonate] to give the surface-bound monosubstituted species Ln(nta)(3)(H(2)O)(L ''). The residual coordinated water molecules were subsequently replaced by pyridine (py) or methyl phenyl sulfoxide (mpso) to give immobilised Ln(nta)(3)(py)(L '') and Ln(nta)(3)(mpso)(L '') species. Photoluminescence studies were carried out at room temperature and 14 K. The emission spectra of the Eu-modified materials were dominated by the typical EU(3+) red lines ascribed to transitions between the (5)D(0) excited state and the ground multiplet ((7)F(0-4)), and only very weak or negligible emission from the organic ligands are observed. Variation of the excitation wavelength confirmed that all of the Eu(3+) ions occupied the same average local environment within each sample. By comparison with the photoluminescence data for the nonsupported Eu(nta)(3)(py)(2) and Eu(nta)(3)(mpso)(2) complexes, it is shown that the interaction between the host and guest has a strong effect on the excited states of the organic hgands; Eu(3+) sensitisation occurs exclusively through the ligands rather than by direct intra-4f(6) excitation. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).
publisher	WILEY-BLACKWELL
issn	1434-1948
year published	2008
issue	24
beginning page	3786
ending page	3795
digital object identifier (doi)	10.1002/ejic.200800367
web of science category	Chemistry, Inorganic & Nuclear
subject category	Chemistry
unique article identifier	WOS:000258855900005