The Influences Of Substituent Of Ligand, Metal Ion And Solvent On The Structure Of Coordination Polymer

In this work,18 coordination polymers have been synthesized with Zn²⁺,Mn²⁺,Cu²⁺, Co²⁺ and Ni²⁺ ions and aromatic carboxylates by hydrothermal,solvothermal and other methods,and the structures and properties of the products have also been investigated. The influences of substituent of ligand,metal ion and solvent on the assembly rules of coordination polymers have been systematically discussed based on the relationship between reaction conditions and products.The thesis includes six aspects as following:1.Three coordination polymers have been synthesized with Zn²⁺ion at the presence of pyridine,by changing the substituents at the 5-position of isophthalic acid under hydrothermal condition.The result shows that when the 5-position of isophthalic acid is substituted with -OH or -tert-Bu,the average coordination number of Zn²⁺ ions and the dimensionalities of these products decrease gradually. It seems reasonable to conclude that the tendency is caused by the increase in steric effect of the substituents.2.Four coordination polymers have been synthesized with Cu²⁺ ion,by changing the substituents at the 5-position of isophthalic acid under solvothermal condition. The result shows that when the 5-position of isophthalic acid was substituted with -OH,-NO₂ or -tert-Bu,the structures of these products change from sphere to two-dimension plane structure.It seems reasonable to conclude that the tendency is caused by the decrease in hydrophilicity and the increase in steric hindrance of the substituents,which markedly change the orientations between the secondary bulid units and ligands.3.Two coordination polymers have been synthesized with 5-tert-butylisophthalic acid and 4,4'-bipyridine through self-assemblies under hydrothermal condition by changing metal ions.The result shows that Mn²⁺ ion adopts six-coordinate mode, whereas the Zn²⁺ ion adopts four-coordinate or six-coordinate modes,the structure of Mn²⁺ product is 1D chain,and the structure of Zn²⁺ product is 2D layer,respectively.The differences in the radii and the coordination modes of Mn²⁺ ion and Zn²⁺ ion,result in different structures of coordination polymers.4.Two coordination polymers have been synthesized with 4,4'-biphenylicarboxylic acid by self-assemblies under solvothermal condition by changing metal ions. The results show that the differences in the radii and the coordination modes of Mn²⁺ ion and Co²⁺ ion,result in 3D net structure of Mn²⁺ ion and 2D layer structure of Co²⁺ ion,respectively.5.Three coordination polymers have been synthesized with Co²⁺ ion and 2-nitroterephthalic acid in different solvents(DMSO,water and mix-solvents of H₂O and DMA).The results show that polarity,coordination capability and steric hindrance of solvents determine the structures of the coordination polymers.6.Two coordination polymers with iso-structures have been synthesized with 2,6-naphthalenedicarboxylic acid and Co²⁺ ion in different solvents(DMA and NMP).The results show that coordination polymers synthesized in DMA or NMP have the similar structures,because the tow kinds of solvents have similar polarity,coordination capability and steric hindrance,they have similar structure directing effect on coordination polymers.