Synthesis, Characterization And Properties Of Metal Complexes Derived From Antipyrine

Due to the flexibility of the structure and functional group, Schiff base-derived metal complexes exhibit unique material physical properties such as light, electricity, magnetic and good coordination chemistry properties, which have attracted the researcher’s considerable attention. More novel functionality would be endowed to the target schiff base complexes by designing of new 4-aminoantipyrine-based ligands with special functional groups and by selecting various metal ions. Therefore, investigation on the synthesis and properties of new schiff base ligands and complexes has great significance in the development of coordination chemistry.By condensation of 4-aminoantipyrine and different aldehydes (pyridine-4-formaldehyde, pyridine-3-carboxaldehyde, salicylic aldehyde),3 kinds of schiff base ligands were synthesized. Using 3 kinds of schiff base ligands in some reaction conditions and transition metal reaction,26 kinds of not reported metal complexes were synthesized, and their single crystal structure analysis and the system research were performed by X-ray powder diffraction, infrared spectroscopy, Raman spectroscopy, thermogravimetric analysis and fluorescence and magnetic analysis, structure characterization and properties were studied for the obtained complexes. This thesis mainly studied the synthesis of 4-aminoantipyrine-derived metal complexes, with the aim to explore their coordination ways and spatial structure characteristics and the law and to establish the structure-property relationship. Further study on the 4-aminoantipyrine of schiff base structure characteristics of schiff base metal complexes with fluorescence and magnetic properties. As long as the results obtained as follows:1. Schiff base compounds as the main ligand, all sorts of lunar calendar ion or solvent molecules for the auxiliary ligand ions, under the condition of low-temperature hydro/solvothermal synthesis, centered on the first, second and third transition metal complexing ions, successful synthesis of the high rate of 26 new transition metal complexes, composed of a 4-aminoantipyrine-derived schiffs base functional metal complexes of small database, enrich the 4-aminoantipyrine-derived schiffs base functional complexes of ligand and structural chemistry theoretical basis.2. By condensation of 4-aminoantipyrine and pyridine-4-formaldehyde (L4) as the main ligand, seven kinds of transition metals and M(M= Zn2+and Cd2+, Mn2+, Co2+, Pb2+ and Ni2+ and Cu+) ions for the center,13 Schiff base metal complexes have been synthesized such as [Zn(L4)(NO3)2]n (1), [Zn(L4)2(NO3)2(H2O)]n (2), [Cd(L4)2(NO3)2]n (3), [Pb(L4)2CNO3)2]n (4), Zn(L4)Cl2(CH3CH2OH)]n (5), [Zn(L4)Cl2(CH3OH)]n (6), [Zn(L4)Br2]n (7), [Cu(L4)Cl] (8), t(CuBr)2(L4)]n (9), [(CuCl2)-[HL4)+]n (10), [Mn(L4)Cl2(CH3CH2OH)] (11), [Co(L4)Cl2(CH3CH2OH)]n (12), [Ni2(L4)4Cl4·2(H2O)·2(CH3CH2OH)] (13). Structure analysis showed that the ligand L4 tends to form the coordination polymer chain structure, in the synthesis of 13 kinds of complexes,76.9% of the complexes formed polymer chain structure, only three cases form discrete dinuclear complexes [Cu(L4)Cl], [Mn(L4)Cl2(CH3CH2OH)] and [Ni2(L4)4Cl4-2(H2O)·2(CH3CH2OH)]. Show that ligand L4 can be used as a building a one-dimensional polymer chain specificity ligand. Directional synthesis for the special structure of functional coordination has strong guiding significance.3.13 schiff base complexes crystal structure characteristics:the complex [Zn(L4)(NO3)2]n crystallize in the Orthorhombic, with space group being Pbca. The compounds [Zn(L4)2(NO3)2(H2O)]n、[Zn(L4)Br2]n、[Mn(L4)Cl2(CH3CH2OH)] belong to triclinic and their space group are all P-1. In addition, the other complexes belong to monoclinic system with space group being P21/n, P21/c, Cc or C2/c. Due to the diversity of the metal ions and ligand compounds show the diversity of coordination:for example, in complex [Zn(L4)(NO3)2]n, the central Zn atom is five-coordinated with triangle bipyramid geometry, through the bridging ligand L4 formed a one-dimensional chain structure. In compounds [Zn(L4)2(NO3)2(H2O)]n、 [Cd(L4)2(NO3)2]n、[Mn(L4)Cl2(CH3CH2OH)]、[Ni2(L4)4Cl4·2(H2O)·2(CH3CH2OH)], the central atoms are six-coordinated with the distorted octahedral geometry configurations. In Compound 4 the central Pb atom is eight-coordinated with distorted dodecahedron’s geometry configuration. Center of metal coordination diversity enriches 4-aminoantipyrine-derived schiffs base metal complexes of coordination chemistry.4. By condensation of 4-aminoantipyrine and pyridine-3-formaldehyde(L3) as the main ligand, anionic NO3-, Br- and I" as the auxiliary ligand, four new complexes such as [Zn(NO3)2(L3)]n(14)、[Cd(NO3)2(L3)2]n(15)、[ZnBr2(L3)]n(16)、[ZnI2(L3)]n(17) were synthesized under the certain solvothermal conditions. X-ray crystal diffraction shows that the four complexes are in one dimensional chain polymer structure, this kind of compound structure of one dimensional small degree under the influence of metal ion type, auxiliary anion. But there are some differences between crystallographic characteristics, such as:metal Zn(Ⅱ) of the [Zn(II)X2L3]n (X=NO3-,Br�'�I-) compounds are in monoclinic system P grid space group of crystal, and assembly for the center with metal Cd(Ⅱ) complexes formed by [Cd(NO3)2(L3)2]n belongs to triclinic crystal system P-1 space group. In addition, in the center of the four complexes ligand and metal ion Zn(II) and Cd(Ⅱ) coordination space configuration also presents the differences:In compounds [Zn(NO3)2(L3)]n and [Cd(NO3)2(L3)2]n, the central Zn and Cd atoms are all six-coordinated with distorted octahedron geometry configurations. In compounds [ZnBr2(L3)]n and [ZnI2(L3)]n the central Zn atoms are all four-coordinated with slight deformation of the tetrahedron geometry configurations.5. By condensation of 4-aminoantipyrine and salicylic aldehyde (HL5) as the main ligand, anionic NO3-,Cl- and Ac- as the auxiliary ligand, eight different new metal complexes were synthesized. Because HL5 ligand coordination atoms in space arrangement lead to phenyl phenol hydroxyl oxygen it is difficult to bridge the one-dimensional polymer structure formation, HL5 with the first transition of divalent metal M(II) (M=Zn, Mn, Co, Ni) ligand dinuclear metal Coordination compound formation, [Zn2(L5-)2(NO3)2] (18), [Co2(L5-)2(NO3)2] (20), [Ni2(L5-)2(NO3)2-(CH3OH)] (21), [Mn2(L5-)2Cl2·2(H2O)] (22), [Co2(L5-)2Cl2·2(H2O)] (23), [Ni(L5-)Cl·2(CH3OH)] (24), [Mn2(L5")2(AC)2] (25), and transition metal Pb(H) assembly is formed after the quad-core metal complexes [Pb4(L5-)4(NO3)4·2(CH3OH)] (19). Crystallography studies have suggested that the ligand HL5 metal coordination compound formation, give priority to with discrete dual-or polynuclear metal, crystal complexes also crystallization in triclinic crystal system P-1 space group and monoclinic system P lattice space group.6. In all the complexes are widely including elemental analysis, IR, Raman, solid fluorescence and thermal weightlessness, X-ray powder diffraction characterization, structure and properties such as compounds and explore the relationship between structures and properties.7. Determination of all the dual-core 4-aminoantipyrine magnetic properties of metal complexes, the results show that the different dual-core atom complexes exhibit different magnetic characteristics in different configurations, such as complexes [Co2(L5-)2(NO3)2] in the two Co(Ⅱ) show the ferromagnetic interactions between atoms, [Ni(L5-)Cl-2(CH3OH)] of two metal Ni(Ⅱ) exists antiferromagnetic interaction between atoms and two complexes have almost the same superexchange function channel, square piece of configuration of the former Col-02-Col-02 and the latter the four corners of the block configuration Nil-O2-Nil-O2 is almost exactly the same bond length and bond Angle, but have different magnetic characteristics, the former has stronger ferromagnetic effect, while the latter has stronger antiferromagnetic interactions. This may be related to its effect of ginger-Taylor, the former of Co2+ have d7 electronic configurations:(t2g)5(eg)2, while the latter Ni2+ have d8 electronic configurations: (t2g)6(eg)2, octahedral distortion of the former is more obvious, therefore, the former have ferromagnetic effect,the latter has a antiferromagnetic function. To realize the coordination between different structure and magnetic controlled synthesis and screening for new type of magnetic functional complexes certain theoretical basis.8. The determination of the schiff base ligands and their part of the fluorescence properties of the metal complexes. [Zn(L4)(NO3)2]n, [Cd(L4)2(NO3)2]n, [Pb(L4)2(NO3)2]n, Zn(L4)Cl2(CH3CH2 OH)]n,[Zn(L4)Br2]n, [Zn2(L5-)2(NO3)2], [Pb4(L5)4(NO3)4·2(CH3OH)] seven complexes with good fluorescence properties. Compared with the ligands, the fluorescence intensity enhanced obviously, emission peak position have taken place in a certain degree of blue shift. For example:4-aminoantipyrine-derived metal complexes show fluorescence emission, mainly is the electron transfer between the metal-ligand (MLCT) and the electron transfer between ligand and metal (LMCT) and electron transfer between ligand and ligand (LLCT).The innovation points of this paper are as follows:1. By designing aminoantipyrine-derived ligands with diverse coordination sites, one-dimensional and zero-dimensional novel functional Schiff base metal complexes were designed and assembled selectively.2. By using self-synthesized Schiff base complexes and choosing suitable derived metal,26 types of novel mental complexes were synthesized. A new train of thought was provided to overcome the unpredictability of target products by hydrothermal and solvothermal method.3. A small database involved 26 new transition metal complexes of aminoantipyrine-derived ligands was built with abundant structural features. The relationships between structures and the optical and magnetic properties of metal complexes were investigated systematically.