A Study On Design, Synthesis And Theoretical Calculation Of V-tape Organic Building Block Together With Its Complexes

In the realm of supramolecular chemistry, great interest has recently been focused on the crystal engineering of coordination frameworks due to their intriguing architectures, new topologies, intertwining and isomer phenomena and their potential applications in microelectronics, nonlinear optics, molecular selection, ion exchange, catalysis and magnetic materials. Lately, it is demonstrated that considerate selectively controlling inorganic building units and creating strategies of assembly is the key in constructing target polymers, which is a most challenging issue facing scientists either. On the guide of principles in molecular synthesis, in this thesis, two new V-shape dipyridylamine ligands were designed and synthesized, and their properly coordination modes were forecasted by theoretical calculation. The effect of the coordination number of metal centers, the isomerlization and conformations of ligand on the complexes' structures were investigated.As a result, eight supramolecule complexes ({[Ag(L₁)₂]NO₃}_n(2), {[Ag(L₁)₂] NO₃}_n.2H₂O(3), [Cu(L₁)₂(COOH-CH=CH-COO)₂H₂O].2H₂O(4), {Cu₂[O₂CC(CH₃) =CH₂]4(L,)}_n(5), [Cu₂(CH₃COO)₄(L₁)]_n(6), Cu(L₁)₄)(CLO₄)₂.2CH₃CH₂OH(7), [Ag (L₂)₂]NO₃(8), [ZnCl₂(L₂)₂](9)) were obtained. In the different reactive conditions, ligand L₁(1) coordinated to metal silver (I) resulting in two different structural complexes 2 and 3. They are two-dimension supramolecule constructed by homo-chiral and heter-chiral helical chains, respectively. Ligand L₁ coordinated to the organic and inorganic copper (II) salt producing three complexes 5, 6 and 7. Because of the different coordination modes of ligand in three complexes, the complexes 5 and 6 are one-dimension coordination complexes with paddle-wheel type and complex 7 is a two-dimension supramolecule. Ligand L₁ coordinated copper (I) forming a three-dimension supramolecule with open hydrophilic tunnels. On the other hand, when we select ligand L₂ reacted with d¹⁰ metal Zn and Ag, the products are double helical and wavilness supramolecules 8 and 9, respectively. In addition, we studied the magnetic behavior of complexes 5 and 6, and on the DFT theory level, investigated the quantum chemistry of supramolecule 7, 8 and 9.