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 fluorescent p-extended indenopyrido[2,1-a]isoindolone derivatives prepared by a palladium-catalyzed cascde reaction

A new family of heterocyclic pentacyclic compounds have been prepared by a cascade reaction involving 2,5-dihalopyridines and (2-formylphenyl)boronic acids. Most of the compounds exhibit high quantum yields of fluorescence in dichloromethane. In some cases, small changes in the substitution pattern caused fluorescence quenching. To rationalize this effect, a detailed photophysical study combined with electrochemical and computational studies was performed on four representative derivatives. It appears that the fluorescence quenching is caused by a thermally activated non-radiative deactivation process that can be prevented in a rigid matrix such as ethanol at 77 K or a PMMA polymer

Multinuclear NMR study of the solid electrolyte interface on the Li-FeSn2 negative electrodes for Li-ion batteries

The composition of the solid electrolyte interface (SEI) layer on the Li-FeSn2 negative electrode has been determined by a multinuclear solid state NMR study. The strong e-nuclear dipolar and contact interactions between the as-formed superparamagnetic Fe nanoparticles and the SEI layer allows a layer wise observation highly depending on the proximity. Li+ from LiPF6, which is traditionally considered as a postdeposited product from the electrolyte solution,has been observed as presenting different solvation states by 19F → 7Li cross polarization magic angle spinning (CPMAS) NMR. Direct contact between LiOH and LixSn or Fe nanoparticles is suggested by Fermi-Contact shifts of −11 and −2 ppm observed in 7Li and 1H NMR spectra, respectively. The LixSn alloy signal remains invisible to 7Li NMR due to the close proximity to the Fe nanoparticles. Effects of different discharging rates and aging at the discharge state are discussed as well

Application of Mössbauer Spectroscopy to Li-Ion and Na-Ion Batteries

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