Synthesis, Crystal Structures And Properties Of Porous Coordination Polymers With N-containing Heterocyclic Ligands

This work focuses on the novel porous coordination polymers (PCPs) based on small simple N-containing heterocyclic ligands with low symmetrical (2-hydroxy- nicotinic acid, 2,2'- bipyridine-3,3'-dicarboxylic acid) and with high symmetrical (1,2,4-triazole, tetrazol-5-amine). Interesting template effect by guests during the template syntheses have been found and examined. In addition, the interactions and correlations between PCPs and guest molecules also have been examined, may propose some new methods and thoughts in the self-assembly and controlled design of PCPs through template syntheses. The thesis is divided into five chapters.In Chapter 1, the study background of this work is concisely introduced with the emphasis on the current survey of PCPs and the driving force in PCPs. Still the interactions and correlations between PCPs and guest molecules also have been briefly reviewed. In addition, the meaning and the progress of this work also have been summarized.In Chapter 2, the study focuses on the self-assembly of alkali metals ions and series M(II)-H2nicO (M(II)= Mn(II) /Fe(II) /Co(II) /Ni(II) /Zn(II) and Cd(II), H2nicO=2-hydroxy- nicotinic acid) under hydro(solvo)thermal conditions or traditional conditions. The rule of the self-assembly have been found via designed logical parallel experiment. Force on the relationship between the Na(I) and series M(II)-H2nicO, The rule can be divide into two points: 1) Without Na(I), whether other alkali metals ions presence or no, only the mononuclear (0D) or zigzag chain (1D) were got; 2) With the presence of Na(I), the series noncentro-symmetric space group 3D PCPs basic on the Na(I) bridged were found. In other words, the series 3D PCPs have high ionic selectivity. Also the series 3D PCPs depend upon the Na(I).In Chapter 3, focuse on the novel PCPs based on small simple N-containing heterocyclic ligands with high symmetry (1,2,4-triazole, tetrazol-5-amine) and d10 M(II) (M(II)=Zn(II) / Cd(II)). With the emphasis on the template effects of guest during the synthesis. Counter ions, solvents, the ratio of reactants and pH value have different extent effects on the structures of the complexes. Additionally, topology analysis have been carried out and examined.In chapter 4, the decarboxylation of H2bpdc (2,2'-bipyridine-3,3'-dicarboxylic acid) under hydro(solvo)thermal condition have been carried out and examined. In the presence of Cu(II) ions, the H2bpdc ligands lost its carboxyl group, while it did not lose carboxyl group in the presence of other transition metal ions. This indicates that Cu(II) ions play a unique catalytic role in the decarboxylation procedure. In addition, one novel porous coordination polymer which contains a supramolecular channel was synthesized with templating by the DMF.