Synthesis, Structures And Properties Study Of Novel Coordination Polymers Based On Tr(?)ger’s Base

The rational design and synthesis of coordination polymers is of significant interest currently, not only due to their enormous variety of interesting molecular architectures and topologies but also because of their potential applications such as gas adsorption, catalysis, ion exchange, magnetism, photoluminescence. However, Featuring special rigidity andA-shaped steric configuration, Troger’s Base (TB) has few researches on the field of coordination polymers; The high steric shindrance of TB tends to form coordination polymerswith high porosity and high surface areas. According to this idea, we decide to combine the TB scaffold with carboxylate groups in order to illustrate a way to extend the applications of Troger’s Base compound into the area of coordination chemistry. The organic ligands containing two or more carboxylate groups offer great potentials for fine control over coordination architectures and have changeable coordination fashion. In this dissertation, we try to achieve directional functional synthesis of the coordination polymers by altering the basic unit:the metal ions and the organic ligands. The main contents are as follows:1. The rigid organic ligand containing two dicarboxylic group H2TBDA based on Troger’s Base has been synthesized and coordinated with three different transition metal ions to construct three novel coordination polymers{Zn(TBDA)·H2O}∞,(1),{Co(TBDA)-H20}∞(2) and{Mn(TBDA)H20}∞(3) under solvothermal conditions, they belong to the same crystal structure by X-ray single crystal diffraction. Two M(II) and four organic ligands make up a paddle-wheel M2(COO)4unit and then extend to a infinite1D beaded chain that is interconnected by types of extramolecular hydrogen bonding to form a three dimensional (3D) supramolecular networks.2. Using the lanthanide metal Ce(∞) instead of transition metal ions,{[Ce6(TBDA)8·NO3-2H2O][-Ce-DMAC·6H20]}∞(4) was synthesized under solvothermal conditions based on H2TBDA ligand. X-ray single crystal diffraction shows that complex (4) displays different coordination configuration of central ions and different types of TB organic ligands. The metal ion is connected by catboxyl bridge to form a wavelike chain and then produce a3D framework via A-shaped steric configuration TB scaffold. Comparing with transition metal ions, lanthanide metal ions of high coordination number tend to forming high dimensional networks. Additionally, a single crystal to single crystal phase transformationwas observed through vacuum activation.3. For the sake of regulating and controlling the intensity and flexibility of coordination polymers as well as to enlarge the porosity, a novel organic ligand H2TBCP is synthesized by the benzene ring modified to the H2TBDA-The phenyl can adjust it steric configuration according to the coordination environment. In combination with Zn(II),{[Zn(TBCP)H20]-DMF}∞(6) is produced under solvothermal conditions based on H2TBCP. Unexpectedly, it shows a1D Loop chain type and is interconnected by types of extramolecular hydrogen bonding to exhibit3D supramolecular network.