Thèse doctorat : Chimie : Strasbourg 1 : 2007. / Titre provenant de l'écran-titre. Bibliogr. 2 p.

Luminescent lanthanide complexes have been widely studied for various biotechnology and materials science uses, however, the application of these luminescent systems in metallopolymers has been relatively limited, especially when compared to those incorporating transition metal complexes. The unique and interesting photophysical properties of lanthanide complexes (i.e., high color purity and long radiative lifetimes) make these systems ideal for the development of luminescent metallopolymers, which are a unique class of hybrid materials that synthetically incorporate metal centers into organic polymers, thereby taking advantage of the beneficial properties of both traditional inorganic (i.e., catalysis, optics, electronics) and organic (i.e., easy to process, flexible, low weight) materials. A new class of lanthanide complexes exhibiting metal-based visible and near-IR photoluminescence has been designed, synthesized and fully characterized by melting point, ESI-MS, elemental analysis and single crystal and powder X-ray diffraction (when possible). The photophysical properties of these luminescent monomer complexes were studied in solution and the solid state, with the emission spectra displaying the characteristic line-like emission peaks of the trivalent lanthanide ions. This indicates efficient energy transfer from ligand centered excited states to the emissive excited states of the lanthanides. The monomer complexes have been electropolymerized, resulting in conducting metallopolymers that display metal-based photoluminescence. Because these hybrid materials retain the desirable properties of both inorganic semiconductors and organic polymers, such as near metallic electrical conductivity, ease of processing, flexibility and light weight, they are promising for applications in solid-state lighting. / text

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Luminescent lanthanide complexes are gaining an increasing amount of interest for their applications in various fields such as OLEDs, immunoassays, analytical sensors, and optical communication. They are promising candidates as light-emitting materials in OLEDs to overcome the difficulty of obtaining pure emission colors with conjugated polymers or small organic molecules. N,N-di(pyridin-2-yl)quinolin-8-amine, a novel blue-emitting ligand, was synthesized to coordinate to europium(III). Experimental studies led to insights of its reactivity with europium acetylacetonate complexes. A new Eu(III) complex based on the diazafluorene ligand was synthesized. A sharp emission band was observed, demonstrating that the Eu(III) ion was effectively sensitized by the intramolecular energy transfer of the ligand. Sensitization of europium(III) by the 3MLCT energy based on an iridium complex-ligand in a d-f bimetallic assembly was previously found to emit red light when irradiated with sunlight. 1-(quinolin-8-yl)butane-1,3-dione, a novel bridging ligand, was synthesized to prepare Eu-Ir complexes with potentially enhanced efficiencies.

Luminescent lanthanide complexes are gaining an increasing amount of interest for their applications in various fields such as OLEDs, immunoassays, analytical sensors, and optical communication. They are promising candidates as light-emitting materials in OLEDs to overcome the difficulty of obtaining pure emission colors with conjugated polymers or small organic molecules. N,N-di(pyridin-2-yl)quinolin-8-amine, a novel blue-emitting ligand, was synthesized to coordinate to europium(III). Experimental studies led to insights of its reactivity with europium acetylacetonate complexes. A new Eu(III) complex based on the diazafluorene ligand was synthesized. A sharp emission band was observed, demonstrating that the Eu(III) ion was effectively sensitized by the intramolecular energy transfer of the ligand. Sensitization of europium(III) by the 3MLCT energy based on an iridium complex-ligand in a d-f bimetallic assembly was previously found to emit red light when irradiated with sunlight. 1-(quinolin-8-yl)butane-1,3-dione, a novel bridging ligand, was synthesized to prepare Eu-Ir complexes with potentially enhanced efficiencies.

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The object of this thesis is to explore functionalized linear dicarboxylate ligands for constructing luminescent metal-organic framework (MOF) sensors. The first series of ligands developed is based on functionalized (E)-4,4'-(ethene-1,2-diyl)dibenzoic acids. Luminescent MOFs have been synthesized from these ligands and their porosity, thermal stability, luminescent properties have been discussed. The second series of ligands is based on functionalized [1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid. Ligands bearing methyl, methoxyl, thioether, aldehyde, ketone, quaternary ammonium side chains have been synthesized and constructed into luminescent MOFs. Their structures, thermal stability, luminescent properties, solvent-dependent luminescence and the underlying mechanisms have been discussed. Vapor sensing experiments have been conducted with MOFs bearing ether and thioether side chains and strong luminescence turn-on is triggered by certain solvents. The MOF with ether side chains has been further tested as sensor slides to evaluate its response rate and recyclability.