Nitrile Containing Nitrogen Heterocyclic Complexes Of Self-assembly And Cycloaddition Research

In this paper, three different series metal-organic coordination based on transition metal ions (ZnⅡ,MnⅡ,CoⅡ,NiⅡ,CuⅡ,FeⅡ) and organic compounds which contain cyanogroups and nitrogen heterocyclc rings are reported. Furthermore, the structures of all these compounds were determined by X-ray single crystal diffractometer, and some properties of those complexes have been characterized by Elemental analysis, Thermal analysis, Infrared spectra, Fluorescence spectra, Ultraviolet spectrum, and X-ray powder diffractometer.First, three new letrozole complexes{[Cu(Le)4C2]·(H2O)}(1),{[Ni(Le)4Cl2]·(H2O)}(2) and {[Co(Le)4Cl2]·(H2O)}(3)(Le=Letrozole=1-[di(4-cyano phenyl) methyl]-1,2,4-triazole) were obtained from self-assembly of Cu", Ni" and Co"with medicine letrozole. The local geometry around central metals can be best described as a dreich octahedron which constructed by two chlorine atoms and four monodentate nitrogen atoms from different letrozole ligands. The molecular skeleton was linked by some hydrogen bonds to form a one-dimensional structure. We found that the change rule of unit cell volume could be explained by periodic law of elements. Furthermore, the thermostability and optical properties of them were studied.Second, we obtained two novel milrinone compounds [(Mi)-H2O](4) and [(HMi)-C104](5) from solvothermal method in the presence of MgCl2·6H2O, Fe(ClO4)3·6H2O and milrinone. The two compounds were composed of ligand molecules and free small molecule(water or perchloric acid). The molecular skeleton was linked by hydrogen bonds to form a one-dimensional structure.Third, three new complexes containing milrinone tetrazolyl ligands were prepared. In situ [2+3] cycloaddition reactions of milrinone with sodium azide, and using MnCl2·4H2O, CoCl2·6H2O or FeSO4·6H2O as a Lewis acid respectively,(Demko-Sharpless tetrazole synthesis method) under hydrothermal reaction conditions gave{[Mn(Mitz)2(H2O)2]·(H2O)}(6),{[Fe(Mitz)2(H2O)2]·(H2O)}(7),{[Co(Mitz)2(H2O)2]·(H2O)}(8). The central metals in these complexes were six coordinated, which connected by two water molecules, two nitrogen atoms from different tetrazolyl groups and two oxygen atoms from carbonyl respectively. The framework is linked by these hydrogen bonds to form a two-dimensional structure. Besides, we analyzed the fluorescence and thermostability of them.Moreover, a three dimensional complexes [Zn(Mit2)2(H2O)]n(9) were obtained by in situ synthesis of milrinone tetrazolate. The local geometry around central metal can be described a distorted tetrahedron which constructed by two nitrogen atoms from different tetrazolyl groups, one nitrogen atoms from pridine ring and a water molecule. The result of thermogravimetric analysis found that the compound was pediocratic.