Syntheses, Structures And Properties Of Magnetic Complexes Based On Metal Chains

Recently, metal-organic compounds have attracted chemists' and material scientists' attention due to their application in the fields of optical, electronic, magnetic and so on. Meanwhile, the application of hydro(solvo)thermal and ionothermal methods in the synthesis of metal-organic compounds, inorganic materials and inorganic-organic hybrids make it possible to synthesize more compounds with interesting structures. This dissertation is composed of three chapters, which mainly focus on the study on syntheses, structures and properties of four compounds with magnetic properties.Chapter one, as a preface of the dissertation, mainly includes three parts. One is a brief introduction to the hydro(solvo)thermal, ionothermal synthesis methods and research progress of ionothermal synthesis. The second mainly gives basic theory of magnetism, research progress of the molecular-based magnetic materials especially those showing 3-D M-O-M frameworks. The third is an introduction to the research progress nowadays of metal-organic compounds with ligand 2-amino-5-mercapto-1,3,4-thiadiazole ligand.In chapter two, two compounds, namely [NH4][Co(OH)SO4] (1) and Co3(OH)2(OAc)4 (2), have been obtained by ionothermal treatment of a mixture of CoSO4/Co(OAc)2and [bmim]BF4 (bmim=1-butyl-3-methyl imidazolium). Both compounds show 3-D frameworks. In compound 1, the trinuclear Cobalt (2Co(1) and Co(2)) unit is formed by vertex-sharing of Co(1) and Co(2) octahedra. The units are further bridged by sulphate to form a 2-D layer. The adjacent layers are connected by the Co(2)-O cooridnation bonds to form the final 3-D network.2 is a novel hybrid cobalt hydroxyacetate magnet that contains a 3-D Co-O-Co framework consisting of vertex-sharing octahedral chains bridged by another octahedra via edge-sharing and shows spin glass behaviour. The importance of complex 2 may be reflected by:(1) the magnet is synthesized by non-traditional methods (ionothermal reaction); (2) examples of 3-D M-O-M (M=transition metal) connectivity in hybrid materials are scarce, and they are only described with succinate, glutarate, formate, acetate and aspartate; (3) magneto-structural study of new compounds of 3-D Co-O-Co frameworks remains a challenge.In chapter three, two compounds Cd(AMTD)CI (3) and N(CH3)4[Ni(AMTD)Cl2] (4) are reported through the solvethermal treatment of CdCl2/NiCl2 with heterocyclic ligand HAMTD (2-amino-5-mercapto-1,3,4-thiadiazole), which all show 3-D supramolecular network. In complex 4, [NiCl2N2]∞chains, which are composed of edge-sharing Ni(1)Cl4N2 and Ni(2)Cl4N2 octhedra, are extended via hydrogen bond interactions to a 3-D supramolecular network.