Syntheses And Luminescent Properties Of Organic-Inorganic Coordination Polymers Generated From Fulvene Ligands And Unsymmetrical 1,3,4-Oxadiazole-Containing Ligands

The chemistry of organic-inorganic coordination polymers has recently become area of increasing interest. Self-assembly of organic ligands and inorganic metal ions is one of the most efficient and widely used approaches for the construction of organic-inorganic composite materials. In the thesis, a series of new type rigid conjugated nanometer-sized fulvene ligands were synthesized, furthermore, cyclopenta[d][l,2]pyridazine-containing ligands were obtained by the reaction of the 1,4-diketone group on those fulvene ligands with ArNHNH2. The coordination chemistry of both new types of ligands with transition metal ions were investigated. In addition, two unsymmetrical 1, 3, 4-Oxadiazole-containing ligands have been synthesized, and their coordination chemistry with Cu(II) and Ag(I) was investigated. Totally 12 new coordination polymers were prepared by solution reactions and fully characterized by IR, elemental analysis and single-crystal X-ray diffraction.1.Seven new Ag-containing coordination polymeric compounds generated from the new fulvene ligands with AgClCVHaO and AgSbF6 have been synthesized: Ag(Ll)C1O4-3.5(C6H6) (1), Ag(L2)2SbF6 (2), Ag(L2)2SbF6 (3), Ag(L6)SbF6-H20(4), [Ag2(Lll)(^-C6H6)(H20)](C104)2'(C6H6)-(H20)o.5 (5), [Ag(Lll)]SbF6-solvate (6), [Ag(Lll)](SbF6)2-2C6H6-CH2Cl2 (7). Their Single crystal structures and luminescent properties were investigated in the solid state.2.Two new H-bonded one-dimensional supramolecular complexes, namely Co(L)2(C2H5OH)2(8: L = L2, 9: L = L6) were synthesized by the reactions of CoOAc with fulvene ligand L2 and L6, respectively. Single crystal structures and luminescent properties were investigated in the solid state.3.Two new Cu(II)-containing coordination polymeric compounds based on unsymmetrical 1, 3, 4-Oxadiazole-containing ligands (LI 7), namely [(Cu2(OAc)4)3Cu(OAc)2(L17)4]-2CH3OH-2H2O(10) and [Cu(L17)SO4-2H2O]-H20 (11) were obtained. The first Ag(I)-containing organometallic coordination polymer, namely Ag(L19)OTf (12), was also synthesized by unsymmetrical oxadiazole-containing ligand LI9. Their single crystal structures and luminescent properties were investigated in the solid state.The results reported herein demonstrate that the use of fulvene-type organic spacers and unsymmetrical 1,3,4-Oxadiazole-containing ligands as precursors to bind transition metal ions, is in fact a new and efficient approach for synthesis of novelsupramolecular networks with interesting physical properties.