Study On Solution Synthesis Or Solid Phase Synthesis At Room Temperature, Crystal Structure And Spectra Of Zn(Ⅱ), Ni(Ⅱ) Complexes With Mixed Ligands And Schiff Bases

In this dissertation, Zn(II), Ni(II) complexes with mixed ligands containing nitrogen and oxygen donor atoms and Schiff bases were synthesized by the solution reactions or the solid phase reactions at room temperature. The products were characterized by elemental analysis, IR, NMR, TG and X-ray powder diffraction. A total of eleven crystal structures of these compounds were determined by X-ray single crystal diffraction, among them nine crystal structures were first reported. The dissertation was mainly discussed as follows:Mixed coordination compounds [Zn2(acac)4(ppz)]n, Zn(acac)2(α-AP), Zn(acac)2(QL) and Ni(acac)2(QL)2 were synthesized by the solution reactions in methanol of acetylaceton (acacH) and acetates with piperazine (ppz),a-aminopyridine (α-AP), quinoline (QL), respectively. The complexes M(dien)(NCS)(OAc) (M=Zn, Ni) were synthesized individually via the solution reactions in methanol of diethylenetriamine, ammonium thiocyanate and acetates. The products were characterized by elemental analysis, IR, NMR and TG Their crystal structures were first determined by X-ray crystallography. [Zn2(acac)4(ppz)]n is a new one-dimensional chain binuclear zinc(II) coordination polymer. The two zinc(II) ions are linked by two μ-acetylacetonato oxygen atoms and the separation of Zn-Zn is 3.46A. Each piperazine acts as a bidentate ligand bridged the binuclear zinc(II) complex to form an infinite one-dimensional chain. Zn(acac)2(α-AP) has a one-dimensional chain supramolecular structure formed through hydrogen bonds. The two complexes of M(dien)(NCS)(OAc) (M=Zn, Ni) have three-dimensional network supramolecular structures, which are formed by hydrogen bonds. The central metal ions in above complexes are coordinated by N and O atoms from the mixed ligands. The coordination numbers of these complexes are six or five and the configurations corresponding to these coordination numbers are distorted octahedral and distorted square pyramidal structures.Mixed coordination compounds M(α-AP)2(OAc)2 (M=Zn, Ni) and Zn(Him)2(OAc)2 were first synthesized by the one step solid phase reactions between zinc acetate or nickel acetate and a-aminopyridine, and imidazole (Him) at room temperature without solvent. The reactions were completed in 15 ~ 20 min over 95% yields. The products were characterized by X-ray powder diffraction, elemental analysis, IR,1H NMR and TG. The crystal structure of Zn(α-AP)2(OAc)2 was first determined by X-ray single crystal diffraction. Each Zn(II) ion lies at the center of a distorted tetrahedron composed of two oxygen atoms from monodentate acetate groups and two nitrogen atoms from pyridinerings. Zn(AP)2(OAc)2 has a network structrue formed through intramolecular hydrogen bonds and aromatic-ring stacking interaction.Seven Schiff bases of N-(4-hydroxyphenylmethylene)-l-naphthylamine, N-(4-hydroxyphenylmethylene)-p-methoxyaniline, N-(4-hydroxyphenylmethylene)-benzylamine, N-(4-hydroxy-3-methoxyphenylmethylene)furfurylamine, N-(4-hydroxy-3-methoxyphenyl methylene)-p-methylaniline, N-(4-hydroxy-3-methoxyphenylmethylene)-p-methoxyaniline and N-salicylidene-4-aminoantipyrine were first synthesized by the one step solid phase reactions between aromatic aldehydes with phenolic hydroxyl and amines at room temperature without solvent. The reactions were completed in 15 min with yields over 90%. The products were characterized by X-ray powder diffraction, elemental analysis, IR and H NMR. The crystal structures of N-(4-hydroxyphenylmethylene)-1-naphthylamine and N-(4-hydroxy-3-methoxyphenylmethylene)furfurylamine were first determined by X-ray single crystal diffraction. N-(4-hydroxyphenylmethylene)-l-naphthylamine has a one-dimensional zigzag chain structure formed through intramolecular hydrogen bond and N-(4-hydroxy-3-methoxyphenylmethylene)furfurylamine has a network structrue formed through intramolecular hydrogen bonds. The net charges distributions of N-(4-hydroxyphenylmethylene)-l-naphthylamine and N-salicylidene-4-aminoantipyrine were calculated at the b31yp/sto-3g level. Using the AMl and...