| Coordination polymers not only have variform charming structures, such as1D,2D,3D structures and novel interpenetrating or intertwine structures, but also possess various functions. Design and construction of the metal-organic frameworks (MOFs) have become an attractive prospect for their potential applications in gas absorption, separation, molecular sensing, and catalysis. As we known, the porous shape, dimensions and function groups are key factors for the applications of MOFs, and lots of factors can influence the final structure of MOFs, such as pH values, solvents temperature and so on. Therefore, the targeted design and assembly coordination polymers or MOFs is still a great challenge, which is urgent need to be intensive researched. Besides, the rational selection of metal cations and organic ligands with suitable shape, size, symmetry, functional groups and flexibility is considered to be a pivotal role to construct MOFsIn this dissertation, the1,3-bis(4'-carboxyl phenoxy)benzoic acid (H3cpbda) is choosen as main building block, and successfully construct17coordination polymers. H3cpbda react with different transition metal ions, result various supramolecular isomers and isomorphor. When a series of rigid N-donor ligand is introduced to the react systerm, five vari-dimension coordination polymers are synthesized. The properties and influence factor are intensively discussed. The major contents of this dissertation are listed as follows:(1) H3cpbda reacts with Mn2+, and results a series of supramolecular isomers, by changing the solvent systerms, temperature and reactors. The "T" and "Y" shaped configurations of cpbda3" lead to rectangle and parallelogram shaped1D channel in structures? The solvent void volumes of complex6>1>4>3are according with the solvent molecular size (H2O<MeOH<DMF<DMP) and solvent polarity (H2O> MeOH> DMF> DMP)?The higher molecular size and lower solvent polarity is tending to construct the structure with higher solvent void volume.(2) Hacpbda react with Mn2+and Co2+, and result two groups of isomorphors, by changing the solvent systerms. In the3D structures group, the solvents voids volume of complex6>7>8?Besides, in the2D structures group, the porous size and the solvents voids volume of complex9<10<11. Both the two groups are according with the solvent molecular size (DMF<DMA<DMP) and solvent polarity (DMF> DMA> DMP). Similar to supramolecular isomers, the isomorphors are also keeping the rule that the higher molecular size and lower solvent polarity is tending to construct the structure with higher porous size and solvent void volume. (3) Along with the Cd+and H3cpbda, four rigid N-donor ligands are introduced, and five complexes with different dimensions are successfully constructed. The phen and2,2'-bipy are terminal ligands, which are adverse to increase the dimension of coordination polymers. However,4,4'-bipy and bpe are bridged ligands, tend to assembly high dimension MOFs. Besides, the new type of "M" molecular configuration is a factor to decrease the dimension. The fluorescence researches find that the red shifts are brought out by the introductions of rigid N-donor ligands. The red shift of terminal N-donor ligand is litter than bridged N-donor ligand.(4) Using various synthesis methods, resulting same crystal products. According to the literature, the synthesis methods can bring out the variform crystal morphologies (crystal size and shape). However, the various synthesis ways of complexe in this dissertation are get the similar crystal morphologies and productive rate. It's must bescause of the flexible ligand H3cpbda can adapt the solvent environment and tend to form the similar crystal morphologies.The research of this dissertation provide the theoretical basis for assembly of supramolecular isomers and isomorphors with different structures and functions. |
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