Design, Syntheses, Structures And Properties Of Metal-Organic Supramolecular Complexes With Aromatic Carboxylate Ligands

In recent years, the most important subjects of intensively current research in coordination chemistry, supramolecular chemistry and crystal engineering have focused on building novel metal-organic supramolecular compounds through metal-ligand coordination and intermolecular interactions (hydrogen bonds, Ï€-Ï€ stacking, etc.) between ligands. Design and synthesis of polynuclear, 3d-4f heterometallic and helical metal-organic supramolecular complexes with novel topological structures or special properties are of great interest at present, due to their ability to impart nonlinear optical, electro-chemicals, magnetics, catalysts, molecular devices, highly selective and specific molecular transformations, transport, and storage and polymorphism.However, based on the principles of crystal engineering and supramolecular self-assembly, control of molecular self-assembly to form novel metal-organic frameworks (MOFs) through reacting special ligand with some metal ions and structural adjustment of them by chemical and physical technique have been encountering considerable challenges and opportunities for chemists. With these aims, several carboxylate ligands with N atom are selectively used as building units reacting with 3d or 4f metal ions, and a series of complexes with novel structure have been prepared. Based on crystal diffraction analysis, novel hydrogen bonds (HBs), Ï€-Ï€ stacking interactions and their role in building 0-3 D MOFs and supramolecular isomerism have been studied. The primary investigations on polymorphism, fluorescence properties and cytotoxicity of some complexes have been performed.This thesis covers following five parts:1) In this part the concepts of coordination chemistry, metal organic supramolecular, metal-organic frameworks (MOFs), polymorphism and crystal engineering were simply introduced. The structural research approaches, single crystal growth technology, along with the significance and application of the study, were also discussed. Systematical review on the research background and significances of water cluster, 3d-4f heterometallic and helical metal-organic supramolecular complexes which are related with this thesis were made.2) Boat conformational isomer cis-1 sustained by novel C-H…π(NO₃^-) (delocalized Ï€-electron system) HBs was first obtained within an I-shape tube at low-temperature and transformation of cis-1 to chair conformational isomer trans-2 assembled via multiple C-H … O(NO₃^-) HBs was realized by solvothermal process. The Ag⁺ can enhance the fluorescence of the Tb(III) complex.3) Novel twin chair-like pseudo-decameric water clusters, namely, the dimer of metal bound acyclic water tetramers conformational isomers linked with two O_carboxylate atoms have been observed in complex for the first time. The metal bound acyclic water...