Synthesis, Structure And Properties Of Aldehyde Hydrazine And Hydrazide Metal Complexes

Aldoxime and acylhydrazone ligands are apt to coordinate with metal ions to form stable mononuclear, binuclear and multinuclear metal complexes because of their good flexibility and multiform coordination ability, and one part of multinuclear metal complexes are metallacrowns. Metallacrowns are similar with organic crown, whose metal atoms, hetero atoms or other ions are instead of ring carbon atoms in order to form big ring supramolecular compounds with new function and [M-N-X] repetitive units in structure.They also have broad application prospects in phase activation of the identification of magnetic materials etc. In this view, we studied three oxime ligands and one acylhydrazone ligand reacted with transition and tombarthite metals, 17 complexes were synthesized and characterized by X-ray single crystal diffraction, elemental analysis and FI-IR spectra, three of them are metallacrowns. Properties such as magnetic of the as-synthesized complexes have been systematically studied. The main contents are listed as follows:1.Seven complexes: [Nd2(Hvanox)4(OAc)2(Me OH)2](1), [Sm2(Hvanox)4(OAc)2(Me-OH)2](2), [Pr2(Hvanox)4(OAc)2(Me OH)2](3), [Eu2(Hvanox)4(OAc)2(Me OH)2](4),{[Er3(Hvanox)4(vanox)2(OAc)(Me OH)]}·H2O(5), {[Er6(vanox)2(OAc)14(Me OH)2]}·(H2O)2(CH3CN)2(6), Ni(Hvanox)2(Py)2(7)(vanox=3-methoxy salicylaldoxime), were obtained by the reactions of 3-methoxy salicyla-ldoxime(vanox H2). Complex 1-4 are four similar binuclear lanthanide metal complexes, and all lanthanide cations are adopting distorted tricapped trigonal prismatic coordination environments with nona-coordinated. In the adjacent complex molecules are constructed into 3D network via O-H···O interactions.Complex 5 consists three Er and is constructed into 2D network via C-H···O interactions.Complexes 6 is a hexanuclear 24-MC-6 Er metallacrown, and it is constructed into 3D topological structure via C-H···π and C-H···O interactions, respectively. Complex 7 is a mononuclear nickel complex, and the adjacent complex molecules are constructed into 3D chain structure via C-H···O interactions. Then we studied magnetic properties of 1-6.Studies of the magnetic properties indicate the presence of dominant antiferromagnetic in complex 5 and 6.2. Two complexes:(NMe4)3·[Ni2(3-cooh-5-brsao)2(OAc)(Py)2](8), {[Na Ni3(3-cooh-5-brsao H)2(3-cooh-5-brsao)(NO3)(H2O)4(Py)4]·(NO3)}n(9)(3-cooh-5-brsao-3-carboxyl-5-brominesalicylaldoxime) were obtained by the reactions of 3-carboxyl-5-bromine-salicylaldoxime. Complex 8 is a nickel binuclear complex and each nickel atom is adopting distorted octahedron coordination environments. The adjacent complex molecules are constructed into 2D network via C-H···O interactions. Complex 9 is a sodium-transition metal mixed complex and the adjacent complex molecules are constructed into 1D chain structure via O-Na-O bridge. In complex 9, the adjacent complex molecules are constructed into 3D network via C-H···π interactions. The studies of magnetic properties of9 show that it exhibits anti-ferromagnetic coupling interactions and 8 show that it exhibits ferromagnetic coupling interactions.3. Two complexes: [Ni(sao H)2(4,4’-bpy)2]n(10),(NEt3)·[Fe3O(sao)3(SO4)(Py)3]·(Py)(H2O)2(11)(sao=salicylaldoxime) were obtained by the reactions of salicylaldoxime,.Complex 10 is a nickel mononuclear with two parts named A and B. Each part is constructed into 1D chain structure via 4,4’-bipyridine, and the part B is constructed into3 D network via C-H···O interactions with sigle part A 1D chain. Complex 11 is a 9-MC-3metallacrown, and the adjacent complex molecules are constructed into 2D network via C-H···π interactions. The studies of magnetic properties of 11 show that they exhibit antiferromagnetic coupling interactions.4. Six complexes: Eu(L)(OAc)4Mn2(Me OH)(H2O)3(12), Dy(L)(OAc)4Mn2(Me OH)(H2O)3(13), Tb(L)(OAc)4Mn2(Me OH)(H2O)3(14), [Y2(L)2(OAc)8(OAc)2Mn4(Me OH)(H2O)2]·2Me OH(15), [Cu3(L)(NO3)4(H2O)3]n(16), {[Mn3(L)(OAc)6(Me OH)(H2O)]}n(17)[L=(2-pyridylaldehyde)-2,6pyridyldiacylhydrazone)] were obtained by the reactions of(2-pyridylaldehyde)-2,6pyridyldiacylhydrazone). Complex 12-15 are similar 3d-4f manganese-lanthanide metal mixed complexes, and the center lanthanide atoms are adopting Ln NO8 distorted quadrangular with a single cap in nona-coordinated coordination environments, and the adjacent complex molecules are constructed into 2D network via C-H···O interactions. Complex 16-17 are similar trinuclear transition metal complexes. The adjacent complex molecules are constructed into 1D chain coordinatednitrate ions or hybrid acetate ions, and 2D network via C-H···O interactions. The studies of magnetic properties of 12-17 show that they exhibit antiferromagnetic coupling interactions.In conclusion, we studied three oxime ligands and one acylhydrazone ligand reacted with transition and tombarthite metals, 17 complexes were synthesized and 3 of them are metallacrowns. Properties such as magnetic of the as-synthesized complexes have been systematically studied and the magnetic properties of complexes 5-6、9、11、12-17 show they exhibit anti-ferromagnetic coupling interactions and 8 show that it exhibits ferromagnetic coupling interactions.