Tailored Architectures And Properties Of Nano Porous Coordination Polymers Based On C₃-symmetric Ligands

Porous coordination polymers(CPs) has been widely applied in catalysis, gas storage, sensing and optoelectronic devices and other fields owing to high stability, tailored pore structures and specific properties. Nano- or microscaled coordination polymers are formed using self-assembly of tailored building blocks, and the small size and specific morphology make them enhance performance or explore new properties in compared with bulk coordination polymers. This thesis is focused on the synthesis and properties of nanoarchitectures in coordination polymers based on C3-symmetric ligands including three organic ligands, namely 4,4',4"-benzene-l,3,5-triyl-tribenzoic acid(H3BTB), benzene-1,3,5- tricarboxylic acid(H3BTC), tris(4-(9-phenyl-4,5-DAF)phenyl)amine(TPA-TPTAF). The main contents are as follows.1. MIL-103(Tb BTB) nano/microstructures were successfully synthesized via a facile solvothermal method without template using H3 BTB and Tb(NO3)3·6H2O as the reactants, uniform fluorescent hollow spheres with micropores in thin shells were “one-pot” obtained. The reaction temperature, reaction time, and molar ratio of reactants play important roles in the formation of hollow spherical particles. Meanwhile, a possible Ostawald ripening driven "mass transfer" and "congregate" formation mechanism was proposed. The hollow spheres have intrinsic ?-system of both ?-conjugated ligands and the intermolecular ?-? stacking interactions, and good photoluminescence, which helps it realize an effective detection of aromatic nitro explosives.2. Tb BTC(MOF-76) nanocrystals of nanorods, polyhedron, and spindles were successfully fabricated using H3 BTC and Tb(NO3)3·6H2O by a solvothermal method. SDS(sodium dodecyl sulfate) and other surfactants played a role of tailoring the size and morphology in the reaction. Moreover, thanking to the outstanding photoluminescence, the obtained MOF-76 nanocrystals can be utilized as a sensitive materials for explosive molecules.3. Cu TPA porous spheres and supramolecular gel network were successfully synthesized by the self-assembly of Cu SO4·5H2O and TPA-TPDAF. The species of solvents and different proportions of solvents would affect morphology and size of porous coordination polyers were investigated. And the possible formation mechanism was proposed.