Syntheses, Characteration And Properties Of Organic-Inorganic Coordination Compounds Generated From Bent Ligands And Fulvene Ligands

The chemistry of coordination polymers and supramolecular complexes obtained by self-assembly has recently become area of increasing interest. In this thesis, a series of fulvene ligands, bent ligands bridging by the 1, 3, 4-oxadiazole, 1, 2, 4-triazole and Schiff-base unit were synthesized. The coordination chemistry based on these new ligands and metal ions was investigated. Totally 46 new coordination compounds were prepared and fully characterized by IR, elemental analysis, X-ray single-crystal diffraction and powdered X-ray diffraction. The luminescent properties, reversible ion-exchange, magnetic properties and thermal stability were investigated.I. 13 coordination compounds generated from the 1, 3, 4-oxadiazole bridged ligands and d-block metals have been synthesized. The results demonstrated that the length and bend angle between the two terminal N-donors of the ligands influenced the structures of resulted compounds significantly.II. Symmetrical and unsymmetrical Schiff-base ligands were synthesized and their coordination chemistry with Ag(I), Cu(I), Cu(II) salts was investigated.III. New type of the 1, 2, 4-triazole-bridged ligands were designed and synthesized. Coordination chemistry of the new ligands was investigated, and five Cd and Zn coordination compounds were obtained under different conditions.IV. 10 Ln-based coordination [Ln(H₂O)₈]³⁺@Ln₂L₄ supramolecular compounds and 4 [Mn(H₂O)₆]²⁺@Ln₂L₄ 1-D coordination polymers were synthesized based on ligand-dominated approach. These cage-like complexes are the first family of lanthanide M2L4 nanocages. The solid state luminescent properties, thermal stability and magnetic properties of these Ln₂L₄ complexes were investigated. More importantly, these cage-like complexes can be the host for [Ln(H₂O)₈]³⁺ or [Mn(H₂O)₆]²⁺ cations, and the [Ln(H₂O)₈]³⁺ or [Mn(H₂O)₆]²⁺ guests within these Ln₂L₄ cages are mobile, and are readily replaced reversibly by their analogues with preservation of the original cage structure. The reversible ion-exchange process was proved by the solid state luminescence emission spectra and XRD patterns. This research provides a promising and convenient approach to access to the multifunctional luminescent materials that can provide tunable emissions by controlling the type of guest moieties.V. New type of fulvene ligands containing Schiff-base unit were synthesized. The coordination chemistry of this type of fulvene ligands with Ag(I) was investigated, 8 novel complexes were obtained based on them. This study demonstrated that the use of bent 1, 3, 4-oxadiazole, 1, 2, 4-triazole,Schiff-base bridging ligands and fulvene ligands as precursors to bind transition metal and lanthanide metals, is in fact a new and efficient approach for synthesis of novel supramolecular systems with interesting chemical and physical properties.