Dissertation > Mathematical sciences and chemical > Chemistry > Organic Chemistry > Organic Chemistry general issues > Theory of organic chemistry,physical organic chemistry

Flexible,rigid,Synthesis and characterization of mixed ligand complexes

Author ZhangZuo
Tutor LiuHongKe
School Nanjing Normal University
Course Inorganic Chemistry
Keywords Coordination polymers Hydrothermal synthesis method Flexible ligand Topology Analysis Fluorescence Properties
CLC O621.1
Type Master's thesis
Year 2011
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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.

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