The Synthesis, Structure And Properties Of Hydroxamic Acid Metal Complexes With Benzene Rings And Pyrazole Oxime Rings.

Metallacrowns(MCs), a kind of metallmacrocyclic complexes, resemble organic crowns with metal atoms and heteroatoms instead of ring carbon atoms, and exhibit novel structural motifs and functions. A survey reveals that these cases display special chemical properties, biological activities and magnetic properties, as well as other aspects of concern.Therefore, the synthesis, characterization and properties of such MCs has been one of the focusing fields of scientific research in recent years. Hydroxamic acid ligands contain many N, O donor atoms and present strong coordination ability and modes. The reactions of such ligands and transition metals form many mononuclear or polynuclear complexes,while most of polynuclear display MCs structures with the ring possessing [M-N-O]n connectivity. Herein, amino-anthranilic hydroxamic acid(H2anha), 3-methoxy-benzyl hydroxamic acid(H23-omeshi) and 3-(2-hydroxyphenyl)-5-pyrazol-hydroxamic acid(H3bpa) were chosen to function with the transition metal salts. 11 new complexes including 6 MCs, were obtained, and characterized by elemental analysis, FT-IR spectra and X-ray single crystal diffraction. A Zn complex exhibits novel cubic structure. The corresponding biological activities, magnetic properties and optical properties were explored in the thesis.The main sections of the thesis are as follows:1. Four complexes, [Cu{Cu4(anha)4(NO3)2(DMF)2}]·H2O(1), [Cu{Cu4(anha)4}]·NEt3(2), {Zn4(anha)2[Ph(COO)2]2(OH)2}·2CH3OH(3), [Zn14(anha)12(O)(OH)2(H2O)4](4), were obtained by the reaction of anthranilic hydroxamic acid(H2anha) and different metal salts.Compexes 1, 2, 4 present metallacrowns structures. These complexes have been characterized by elemental analyses, IR-spectrum, spectroscopic analysis and single crystal X-ray diffraction. Complexes 1 and 2 are both 12-MC-4 metalcrowns with Cu ions studding in the centers of rings. Complex 1 show some difference. A one-dimensional chain structure was formed through the linking of two DMF, which form a six-membered chelating ring between two adjacent complexes. Complex 3 is a Zn complex, in which there is anintramolecular ring with a cavity structure. Terephthalic acid anion bridged complexes to form an infinite network structure. Complex 4 is a Zn complex which intramolecular showing a cubic structure. 14 Zn ions occupy the eight vertices and six face-centerd positions, 12 anthranilic hydroxamic acid ligands occupy 12 edge positions, while the six faces of this structure display two different metalcrowns structural types. The studies of vitro anticancer activity reveal that both complexes 1 and 2 show moderate activity, while magnetic measurements reveal the antiferromagnetic coupling between metal centers. The fluorescence properties with complexes 3, 4 show different degrees of blue shift phenomenon. Complexes 4 exists quenching phenomenon in organic solvent of DMF and CH2Cl2.2. Five complexes, [Na2Mn4(3-omeshi)4(Cl O4)2(py)8]·2H2O(5), Mn(3-omeshi H)2(6),[Ni5(3-omeshi)4(OH)2]·NEt3·2H2O(7), [Cu5(3-omeshi)4(OH)2]·NEt3·2H2O(8), Cu(3-omesh H)2(9), were synthesized by using of 3-methyloxysalicylald hydroxamic acid(H23-omeshi) with manganese salts and copper salts. Three of them are metalcrowns. Complex 5is Mn-Na heterometallic complex. Two Na ions are located in the opposite two sides of12-MC-4 metalcrown place, and O atoms bridge Na and ring Mn atoms resulting in a stretched state to both sides. The shortest distance is 5.455? between the center of the ring,which is difficult to embedd inside. Complex 6 is a mononuclear Mn complexe. Mn ion is coordinated with two ligands to form a symmetrical five-membered chelating ring. A two-dimensional network structure formed through by many multiple N-H···O hydrogen bond interactions. Complex 7 is a Ni 12-MC-4 metallacrown. The MC ring cavity encapsulats a Ni ion. 1D chain was formed through the chelating O atoms and the adjacent hydroxyl O atoms, while the 1D chain further constructed to a two-dimensional network structure by hydrogen bonds of C-H···O action between 1D chains. The structure of complex 8 is similar with that of complex 7. Complex 9 is a mononuclear Cu complex, and the structure is the same as complex 6. Magnetic studies of complexes 7 and 8 show antiferromagnetic coupling interaction. Vitro anticancer activity of complexes 7, 8, and 9shows that only complex 9 showed moderate activity for two kinds of cancer cells.3. Two complexes, [Co2(bpa)2(Py)4]·Py(10) and [Mn2(bpa)2(DMF)2]n(11) weresynthesized by using of 3-(2-hydroxyphenyl)-5-pyrazol-hydroxamic acid(H3bpa) with manganese salts and cobalt salts. Complex 10 is a dinuclear cobalt complex, which is consisting of two cobalt ions, ligands and pyridine. There is a cycle ring of[Co-N-N-Co-N-N] with a cavity in the middle. A one-dimensional chain structure was formed by C-H···O weak interactions, while the 1D chain further construct a two-dimensional network structure. Complex 11 is a 1D polymer with the single consisting of a dinuclear manganese dimmers. Such case shows a rotational symmetry reflects state and there is a cycle ring of [Mn-N-N-Mn-N-N]. The linking hydroxyl O atoms of the ligands and Mn atoms form a one-dimensional structure, which further form a two-dimensional network structure. Magnetic studies of complexes 10 and 11 show antiferromagnetic couplings.