Crystal Engineering Of Uranyl And Lanthanide Complexes

Crystal engineering and supramolecular chemistry have the same aim to better understand and finely control the intermolecular interactions, so as to design and build novel crystalline solids. The study on uranyl complexes is centered on the understanding of the interaction between uranyl and organic species, which is the key to the design of uranyl sequestering agents and the construction of uranyl-organic assemblies with distinct structure and properties. The study on lanthanide complexes is driven by the design and building supramolecular edifices and network to meet aesthetic pursuit and urgent application. In this article, one part of the work concentrates on uranyl complexes with non-chromophoric and water-soluble ligands for uranyl photophysics and uranyl sequestration, and another part of work focuses on lanthanide complexes with distinct chromophoric groups towards chirality, stability, luminescence, and sensing applications.In chapter 1, this article briefly presents some understanding on coordination chemistry and discusses the background of research on uranyl and lanthanide complexes in detail.From chapter 2 to chapter 4, we synthesize 3,3’-ureylenedipropionic acid, N-(sulfoethyl)-iminodiacetic acid, and N-substituted short-chain aliphatic bis(oxamate) ligands successively, and then obtain their exclusive uranyl complexes respectively. These complexes feature special synthesis conditions and unique supramolecular structures, thus corresponding to distinct uranyl sequestering performance and uranyl photophysical properties respectively. From these data, we answer theoretical issues with regard to luminescence shift, luminescence quenching, and multi-exponential decay, as well as application issue regarding the sequestration of uranyl ions through selective crystallization of uranyl complexes. However, for an immature field of study, schools of thought contend to flourish.Based on N,N’-methylene-bis(pyridin-4-one), in chapter 5 we construct triple helicate cages with medium lanthanides and polycatenated polymeric networks with medium and heavy lanthanides. The study of this work involves spontaneous resolution and chiral symmetry breaking in the crystallization process, the influence of coordination geometry, the second supeamolecular interaction and heavy halogen atom on lanthanide photophysics, as well as the analysis of energy transfer processes. From a diethylamino modified salen ligand, in chapter 6 we build an supramolecular erbium(III) "square prism" with octahedron metal center, and thereafter assembled a supramolecular aggregate of exo-erbium(III) "double-decker" cations wrapped by an anionic cuprous cyanide network. Both erbium(Ⅲ) complexes show near-infrared (NIR) luminescence under the excitation in the visible light area. This work provides a novel and efficient method for stabilizing and observing non-isolable lanthanide edifices. At last, in chapter 7 we design bis(1H-pyridin-2-one)salen ligands, and succeed in obtaining a double-stranded mononuclear Eu(Ⅲ) complex and a pair of chiral mononuclear Eu(Ⅲ) complexes. Photophysical studies show the particularly efficient sensitization of Eu(Ⅲ) ions by bis(1H-pyridin-2-one)salen ligands. The thin film device fabricated by double-stranded mononuclear Eu(Ⅲ) complex possess excellent vapoluminescent sensing performance towards acid-base vapor. The pair of chiral mononuclear Eu(Ⅲ) complexes display rich circular dichroism signals and true circularly polarized luminescence...