Construction Of Coordinaiton Polymers With Substituted Aromatic Carboxylate Ligands

On the basis of the policy of crystal engineering and constructing strategy, a va-riety of substituted aromatic carboxylic acids were chosen as the building blocks to assembly with metal ions to afford novel topological metallosupramolecular com-plexes. The key points of our research are on the emphasis of synthetic methodology of interesting metallosupramolecular complexes, directional regulation of ligation fa-shion from substituents to ligand, analysis of assembly discipline of topological net-work, and impact of co-ligand to the resultant framework. This thesis consists of five chapters.In chapter 1, the recent research progress of coordination polymers based on aromatic carboxylates was represented and their useful properties on catalysis ability and microporosity were also demonstrated. Then the research significance and main conclusion of this thesis were summarized.In chapter 2, five novel ZnII, CoII, AgI and PbII coordination polymers based on a versatile building block 2,3,5,6-tetrabromoterephthalic acid (H2TBTA) have been successfully assembled, including 1-D polymeric chain motif, 2-D kgd and CdCl2, as well as 3-D (42.84)(43)2(44.64.82)2(45.63.82)2(46.63.8)2 network. In these complexes, all the carboxyl groups were appeared as the deprotonized fashion in a vertical pattern to the central aromatic ring. Single crystal X-ray diffraction studies revealed that mod-ulation of solvent choice made the significant impact on the resultant ZnII networks in the structural direction and template effect function.In chapter 3, on the basis of H2TBTA, by employment of 2,5-bi(4-pyridyl)- 1,3,4-oxadiazole (4-bpo) and its 3-N-donor analogue (3-bpo) into the supramolecular assembly system with metal ions (CoII, NiII, CuII, ZnII, AgI, CdII and PbII), complexes 6-17 featured a variety of interesting structures. Furthermore, analysis of another de-rivative H2BTA related complexes 18 and 19 revealed that the discrepancy of the re-sultant networks may arise from the spatial effect distinction of the substituent at-tached to the aromatic ring and then the coordination modes of the carboxylates.In chapter 4, in order to further study the influence of co-ligands upon the coor-dination network from substituted aromatic carboxylates, 5-sulfoisophthalic acid (5-H3SIP) was utilized to react with metal ions, in virtue of 3-/4-bpo, to afford com-plexes 20?27. Notably, in the self-assembly of 5-H3SIP, CdII and 3-/4-bpo, pH value played the vital role not only to the regulated configuration of 3-bpo, but also to the structural dimension of the resultant frameworks.In chapter 5, 5-bromonicotinic acid (5-BN) and 5-bromonicotinic acid N-oxide (5-HBNO), derivatives of nicotinic acid with 5-Br substituent, were employed to react with CoII, CuII, ZnII and CdII to afford eight novel complexes 28?35, including two unprecedented architectures with (3,5)- and (3,6)-connected net topology. In the po-lymers 28?29 and 30?32, manipulation of specific solvents shows a significant struc-tural direction and template effect to the resultant frameworks, respectively.