Synthesis And Characterization Of Flexible, Rigid Mixed-ligand Complexes

Ten new coordination polymers have been synthesized and characterized in this thesis by using solvothermal methods by reaction of flexible ligands and rigid ligands.Two new Cd(II) coordination polymers, [Cd(BDC)(m-bitmb)(H2O)] (1) and [Cd2(BDC)2(p-bitmb)1.5(H2O)2] (2) have been solvothermally synthesized by reacting cadmium sulfate and 1,4-benzenedicarboxylic acid (H2BDC) with flexible ligands 1,3-bis(1-imidazol-l-ylmethyl)-2,4,6-trimethylbenzene (m-bitmb) or 1,4-bis(1-imidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (p-bitmb), respectively. ComplexⅠhas a 3D 4-connected 66 supramolecular architecture, a distorted diamond structure, formed by two alternate chiral helical chains linking a network, while complex 2 contains 2D (3,4)-connected W-shape-like layers with the novel (63·66) topology. The luminescent properties for the complexes 1-2 in the solid state were all assigned to ligand-to-ligand charge transfer(LLCT).Five homo-and heterometallic coordination polymers with mixed organic ligands:[C30H27CICo2N6O6] (3), [C30H27ClCu0.09Co1.91N6O6] (4), [C30H27CICo1.88CU0.12N6O6] (5) have been synthesized utilizing the 1,3,5-benzenetricarboxylic acid (H3BTC) and 1,3,5-tris(imidazol-1-2,4,6-trimethylbenzene) (titmb). [C27H28CON4O7] (6) and [C27H28Cu0.09Co0.91N4O7] (7) were formed by reacting 1,3,5-benzenetricarboxylic acid (H3BTC) with flexible ligand 1,4-bis(1-imidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (p-bitmb). These complexes have been synthesized and fully characterized by X-ray diffraction, IR, elemental analysis, thermogravimetric analysis, UV-vis, and magnetic measurements. Complexes 3,4 and 5 are isomorphs and each metal-organic frameworks (MOFs) has interesting (3,6)-connected net topology by selfpenetration of two sets of (10,3)-a net with a 3D Schlafli symbol (63)2(612·83) supermolecular architecture, while complexes 6 and 7 are isostructural and contain 2D 4-connected lays with the (44·62) topology. Complexes [C51H62N12NiO2] (8) and [C6oH66Zn3N18O18] (9) were synthesized through solvothermal or evaporation methods and these complexes were characterized by X-ray diffraction.We have also synthesized a M2L2 macrocycle-like complex C36H48AU3Cl3N8O2 (10) with an AuCl2- anion within it.