Highly efficient luminescent hybrid materials covalently linking with europium(iii) complexes via a novel fluorinated [small beta]-diketonate ligand: synthesis, characterization and photophysical properties

A novel highly fluorinated [small beta]-diketonate ligand, 1-(3,5-bis(benzyloxy)phenyl)-4,4,5,5,5-pentafluoropentane-1,3-dion e (HBBPPF) and its corresponding europium(iii) ternary complex, Eu(BBPPF)3(DDXPO) [DDXPO = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene oxide] were synthesized via a dexterously designed routine, characterized and its photophysical properties (PL) investigated. PL measurement results indicated that the europium(iii) ternary complex exhibits intense red emission under UV light excitation with a solid-state quantum yield of 39%. An organic-inorganic mesoporous luminescent hybrid material was also constructed by linking the ternary europium(iii) complex to the functionalized hexagonal mesoporous MCM-41 through the modified [small beta]-diketonate ligand (SiBBPPF-Na). [small beta]-Diketonate grafted to the coupling agent 3-(triethoxysilyl)propyl isocyanate was used as the precursor for the preparation of mesoporous materials. A modified MCM-41 mesoporous material containing ternary europium(iii) complex covalently bonded to the silica-based network, designated as Eu(BBPPF-Si)3(DDXPO)/MCM-41, was obtained by interacting SiBBPPF-Na with europium nitrate, DDXPO and MCM-41 via a ligand-exchange reaction. The new mesoporous hybrid material was characterized by powder X-ray diffraction, nitrogen adsorption-desorption, thermogravimetry, transmission electron microscopy, dynamic light scattering, FT-IR, 29Si CP MAS NMR and 13C NMR solid-state techniques, and photoluminescence spectroscopy. Eu(BBPPF-Si)3(DDXPO)/MCM-41 exhibits an efficient intramolecular energy transfer process from the silylated [small beta]-diketonate to the central Eu3+, namely, the "antenna effect", which favours a strong luminescent intensity (quantum yield = 43%). Thermogravimetric analysis on Eu(BBPPF-Si)3(DDXPO)/MCM-41 demonstrated that the thermal stability of the lanthanide complex was evidently improved as it was covalently bonded to the mesoporous MCM-41 matrix.