Modulating the photoluminescence of bridged silsesquioxanes incorporating Eu(3+)-complexed n,n '-diureido-2,2 '-bipyridine isomers: application for luminescent solar concentrators

Two new urea-bipyridine derived bridged organosilanes (P5 and P6) have been synthesized and their hydrolysis-condensation under nucleophilic catalysis in the presence of Eu(3+) salts led to luminescent bridged silsesquioxanes (M5-Eu and M6-Eu). An important loading of Eu(3+) (up to 11%(w)) can be obtained for the material based on the 6,6'-isomer. Indeed the photoluminescence properties of these materials, that have been investigated in depth (photoluminescence (PL), quantum yield, lifetimes), show a significantly different complexation mode of the Eu(3+) ions for M6-Eu, compared with M4-Eu (obtained from the already-reported 4,4'-isomer) and M5-Eu. Moreover, M6-Eu exhibits the highest absolute emission quantum yield value (0.18 +/- 0.02) among these three materials. The modification of the sol composition upon the addition of a malonamide derivative led to similar luminescent features but with an increased quantum yield (026 +/- 0.03). In addition, M6-Eu can be processed as thin films by spin-coating on glass substrates, leading to plates coated by a thin layer (similar to 54 nm) of Eu(3+)-containing hybrid silica exhibiting one of the highest emission quantum yields reported so far for films of Eu(3+)-containing hybrids (0.34 +/- 0.03) and an interesting potential as new luminescent solar concentrators (LSCs) with an optical conversion efficiency of similar to 4%. The ratio between the light guided to the film edges and the one emitted by the surface of the film was quantified through the mapping of the intensity of the red pixels (in the RGB color model) from a film image. This quantification enabled a more accurate estimation of the transport losses due to the scattering of the emitted light in the film (0.40), thereby correcting the initial optical conversion efficiency to a value of 1.7%.FCT - PTDC/CTM/101324/2008COMPETEFEDE

Highly photostable luminescent poly(caprolactone)siloxane biohybrids doped with europium complexes

In this paper, we propose for the first time that the combination of a sol-gel derived diurethane cross-linked siloxane-based biohybrid host including short poly(ε-caprolactone) segments (PCL(530)) and lanthanide aquocomplexes incorporating β-diketonate ligands yields an effective protecting cage that efficiently encapsulates the emitting centers and reduces luminescence quenching. The results obtained using the Eu(tta) 3 (H 2 O) 2 (where tta - is 2-thenoyltrifluoracetonate) complex demonstrate that 1 (2) carbonyl oxygen atoms of the host matrix enter the Eu 3+ coordination shell, thus replacing the labile water molecule-(s). The significant increase in the quantum efficiency q of the doped hybrid with respect to that of Eu(tta) 3 (H 2 O) 2 (44.2 versus 29.0%, respectively) reveals that complex anchoring to the PCL(530)-based host structure contributes to enhancement of the 5 D 0 quantum efficiency. However, when a complex that contains only strong chelating ligands, such as Eu(tta) 3 phen (where phen is 1,10-phenantroline), is incorporated into the same host medium, the effect is lost and the 5 D 0 nonradiative paths in the doped hybrid are higher than those existing in the complex itself. Under UVA exposure, the emission intensity of PCL(530)/siloxane/Eu(tta) 3 (H 2 O) 2 decreased 10% in 11 h, whereas that of PCL(530)/siloxane/Eu-(tta) 3 phen decreased 25% in the same period of time.Fundação para a Ciência e para a Tecnologia -POCI/CTM/46780/03; POCI/CTM/40063/01.CQ-VR