Tailoring photoluminescence properties in ionic nanoparticle networks.

To investigate the original and promising luminescence properties of ionic nanoparticle networks (INN), various material compositions were investigated. In this work, the linker used to network the silica nanoparticles was varied; numerous substituted or non-substituted imidazolium, pyrazolium and pyridinium linkers are presented. Photoluminescence experiments on the INN hybrid materials revealed strong emission bands over a broad range in the visible region of the light spectrum. Varying the aromatic linker between the imidazolium units induced clear shifts of the emission maxima up to 100 nm, as a consequence of π-π stacking interactions. Steric hindrance and inductive effects of the substituents, introduced on the aromatic units, also strongly influenced the luminescence properties of the materials by modifying the π-π stacking between the imidazolium rings. Small and wide-angle X-ray scattering (SAXS, WAXS) experiments revealed a clear trend between the obtained structural parameters (short-range order parameter and distance of the aromatic units within the hybrid material) and the luminescence quantum yields of the INN materials.

Exploring the molecular structure of imidazolium-silica-based nanoparticle networks by combining solid-state NMR spectroscopy and first-principles calculations.

A DFT-based molecular model for imidazolium-silica-based nanoparticle networks (INNs) is presented. The INNs were synthesized and characterized by using small-angle X-ray scattering (SAXS), NMR spectroscopy, and theoretical ab initio calculations. (11)B and (31)P HETCOR CP MAS experiments were recorded. Calculated (19)F NMR spectroscopy results, combined with the calculated anion-imidazolium (IM) distances, predicted the IM chain density in the INN, which was also confirmed from thermogravimetric analysis/mass spectrometry results. The presence of water molecules trapped between the nanoparticles is also suggested. First considerations on possible π-π stacking between the IM rings are presented. The predicted electronic properties confirm the photoluminescence emissions in the correct spectral domain.

Irreversible thermochromism in copper chloride Imidazolium Nanoparticle Networks.

In this work Imidazolium Nanoparticle Networks (INNs) with chloride counter-ions were used to complex copper dichloride. This complexation reaction leads to the formation of a green material. The properties of the copper INN material were compared to: first, copper imidazolium complexes, without the presence of silica nanoparticles, which are not thermochromic; second, chloride-containing INN material. The copper INN material showed irreversible thermochromic behaviour, with a clear colour change from green to yellow at 180 °C, which is due to a configuration change of the copper complex from planar to tetragonal. This structural change was studied using DSC and in situ SAXS measurements during heat treatment. The thermochromic material is stable under air up to 250 °C. This preliminary study opens the door of optical sensors for INN materials.

Ionic nanoparticle networks: development and perspectives in the landscape of ionic liquid based materials.

This feature article gives an overview of the research performed on ionic nanoparticle networks (INNs). These INNs are hybrid materials consisting of inorganic nanoparticles and ionic linkers, such as imidazolium, bisimidazolium or pyridinium. The synthesis and properties of INNs, for catalysis or sensorics, are presented. At each step INN materials are compared to other hybrid materials of similar composition such as ionogels or suspensions of imidazolium modified nanoparticles.