The Assembly And Properties Of Microporous Coordination Polymers Based On 4-pyridyl -ended Tripodal Ligands Functionalized By Ester Or Amide Group

The construction of porous metal-organic frameworks (MOFs) with nanosized cavities and/or nanosized open channels has attracted significant attention recently due to their potential applications in gas storage, separation,catalysis,and so on. This dissertation reports the construction and properties of a series of coordination polymers based on 4-pyridyl-ended tripodal ligands. The structures have been characterized by single-crystal X-ray diffraction and their sorption properties have been also explored. The results show that:1. The tripodal Ligands BTTP4 containing 4-pyridyl terminal group and its Ag+ complexes have been designed and synthesized. The template effect of anion and solvent molecule on self-assembly of Ag+ complexes has also been investigated. The results indicate that the distinctive structure transformation of are assembled due to difference of size and shape of solvent molecules and anions. In general, the (6, 3) network structures are obtained when using the solvent molecules and anions with relative larger size as template, while 3D networks are found using some smaller templates.2. Two robust porous MOFs containing 1-D channels have been obtained from a tripodal ligand BTTP4 and CuX (X = I or Br). Both of them show selective gas adsorption for CO2 over N2/H2 at low temperature and under atmosphere pressure. In additional, the guest solvents exchange studies imply that the empty framework of complex 10 tends to adsorb aromatic guests.3. Two porous MOFs containing metal-organic polyhedra units have been obtained when pyridine-dicarboxylic acid ligands were selected to react with Cu(NO3)2 and Ni(NO3)2, respectively. Complex 12 reveals selective sorption capabilities for CO2 gas over N2 gases at 273K and 1atm (over 15:1 v/v). The different adsorption capabilities for gases can be ascribed to the existent of a stronger affinity between nanoscopic cage hostes and CO2 guests. In addition, a series of complexes obtained from dinuclear SBUs baseed on single pyridine-dicarboxylic acid ligand display pillared-layer frameworks, which were rarely reported compared with pillared-layer fameworks constructed from mixed ligands.4. When INIA reacted with Zn(NO3)2, the molar ratios of mixed solvent play vital roles in directing the resulting frameworks. A 3D framework 18 containing 1D rod-shaped second building units has been assembled from INIA and Pb2+ ions. More interestingly, this framework exhibits interesting guest-dependent "shrink-swell" behaviors in response to removal and absorption of the guest molecules.