This thesis provides essential information on the systematic design of assembled lanthanide complexes for functional luminescent materials. It discusses the relationships between assembled structures and photo, thermal, and mechanical properties on the basis of crystallography, spectroscopy, and thermodynamics. The described guidelines for assembled structures will be extremely valuable, both for industrial applications and for readers’ fundamental understanding of solid-state photophysics and materials chemistry. Luminescent lanthanide complexes are promising candidates for lighting devices, lasers, and bio-probes owing to their line-like and long-lived emission arising from characteristic 4f–4f transitions. Low-vibrational and asymmetrical coordination structures around lanthanide ions have been introduced to achieve strong luminescence, using specific organic ligands. Recently, assembled lanthanide complexes including coordination polymers and metal organic frameworks have increasingly attracted attention as a new class of luminescent materials offering thermal stability and color tunability. However, improving the luminescence efficiencies of these compounds remains a challenge, and specific molecular designs to control assembled structures and yield additional physical properties have not been established. The author provides a group of bent-angled bridging ligands to boost photoluminescence efficiency, and successfully introduces for the first time glass formability and strong triboluminescence properties.

This thesis deals with strongly luminescent lanthanide complexes having novel coordination structures. Luminescent lanthanide complexes are promising candidates as active materials for EL devices, lasers, and bio-sensing applications. The organic ligands in lanthanide complexes control geometrical and vibrational frequency structures that are closely related to the luminescent properties. In most of the previous work, however, lanthanide complexes have high-vibrational frequency C–H units close to the metal center for radiationless transition. In this thesis, the luminescent properties of lanthanide complexes with low-vibrational frequency C–F and P=O units are elucidated in terms of geometrical, vibrational, and chemical structures. The author also describes lanthanide coordination polymers with both high thermal stability (decomposition point > 300°C) and strong-luminescent properties (emission quantum yield > 80%). The author believes that novel studies on the characteristic structures and photophysical properties of lanthanide complexes may open up a frontier field in photophysical, coordination and material chemistry.

This dissertation, "Synthesis, Structural Characterization and Photophysical Properties of Lanthanide Complexes Containing Polydentate Amide Ligands" by 黎寶韻, Po-wan, Lai, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. DOI: 10.5353/th_b4257618 Subjects: Lanthanum compounds Amides Ligands Photochemistry

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Edited by a highly regarded scientist and with contributions from sixteen international research groups, spanning Asia and North America, Rare Earth Coordination Chemistry: Fundamentals and Applications provides the first one-stop reference resource for important accomplishments in the area of rare earth. Consisting of two parts, Fundamentals and Applications, readers are armed with the systematic basic aspects of rare earth coordination chemistry and presented with the latest developments in the applications of rare earths. The systematic introduction of basic knowledge, application technology and the latest developments in the field, makes this ideal for readers across both introductory and specialist levels.