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.

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.

The use of chiral lanthanide complexes as probes to investigate interactions with other chiral molecules and macromolecules is of particular interest. A key step in the development of such systems is the preparation of a single, rigid enantiomer of the complex which is conformationally rigid on the NMR timescale or the lifetime of the metal-based emission. Chiral europium and terbium complexes are of particular concern as they may function as emissive probes and are amenable to analysis by circular dichroism and circularly polarised lummescence. Charge neutral and cationic complexes of N-substituted 1,4,7,10- tetraazacyclododecane, functionahsed with three phosphmate and one amide pendent arms, or two, three and four pendent amide arms containing a remote chiral centre, have been prepared. The chirality of the remote stereocentre determmes the helicity of the arrangement of the pendent arms and the conformation of the 12-membered macrocycle.The chiral europium and terbium complexes of the tetraamide complexes exist as single, rigid enantiomers, exhibiting a well-defined metal-based circularly polarised emission. Circular dichroism studies reveal that exciton coupling occurs between adjacent pairs of 1-naphthyl chromophores of tetraamides, whereas the constitutional 2- naphthyl isomers exhibit excimer formation. The behaviour of the di-, tri-, and tetraamide complexes in the presence of added anions has been investigated. The measurement of the luminescent lifetime of the excited state and the circularly polarised emission exhibited by the enantiopure complexes in aqueous solution affords a novel way of signalling the presence of selected oxy-anions.

No description available.

Thesis (M.Sc.)--University of Adelaide, Dept. of Physics, 1971.

Thesis (Ph.D.)--Australian National University, 2006.

Thesis (M.S.)--Virginia Polytechnic Institute and State University, 1991. / Vita. Abstract. Includes bibliographical references (leaves 71-75). Also available via the Internet.

Thesis (M.S.)--University of Wisconsin--Madison, 1967. / eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (M. Phil.)--University of Hong Kong, 1994. / Includes bibliographical references.