Syntheses, Structures And Properties Of Metal-Organic Materials Constructed From Manganese And Copper Clusters

In recent two decades, metal–organic materials （MOMs） havebeen developing at an extraordinary pace, with an exponentialgrowth in the number of research papers and reviews appearing inthe chemical literature. Due to the perfect linkage between theinorganic ‘joints’ and organic ‘struts’ by strong coordination bonds,MOMs present topologically diverse and aesthetically pleasingstructures, which lead to lots of major breakthrough applications.In this paper, by using transition–metal clusters as supramolecularbuilding blocks （SBBs） and organic ligands as linkers, elevencoordination polymers have been successfully synthesized bycontrolling the reaction conditions. This dissertation mainlyfocuses on syntheses, structures and properties of these metal-organic polymers with emphases on magnetism or luminescence,which includes four parts as follows:1. The research background of MOMs is fistly introduced in thepreface, in which the design and syntheses of MOMs are conciselysummarized. The role of transition–metal clusters as SBBs is statedfor MOMs based on metal–organic polyhedra （MOPs）. A comparative analysis is made on the difference and relation between two basicMOMs, metal–organic frameworks （MOFs） and supramolecularcoordination polymers （SCCs）. Finaly, a research progress is treatedabout the magnetism of MOFs based on M-L-M （L=single atom）connectivity.2. By using Mn（CH₃COO）₂·4H₂O as Mn（II） source, two3D MOFs havebeen synthesized via tuning the amount of NaOH in the presence ofDMF and CH₃OH, which are based on Mn8metal–organic cube （MOC）as SBBs. Na₄Mn₈（μ4-OMe）6（μ4-MeCO₂）122MeCO₂（1） has a novel bodycentered cubic antiferromagnetic heterometallic coordinationnetwork based on Mn₈@Na₈cube-in-cube SBBs, in which theunprecedented cubic （39.46）8topological Mn8（μ4-OMe）6cube withcapped oxygen of five coordination is firstly revealed.（Me4N）4-Mn（HCO₂）6（2） is a porous framework with a Mn8face-to-face SBBsconstructed from formate and manganese, in which the1D channel issupported by Me4N+cations from in situ decomeposition of DMF.3. Nine polymers [Cu5（OH）3Br3（ina）4]（3）,[Cu₅（OH）₃Cl₃（ina）₄]（4）,[Cu₂（OH）（ina）₂]（5）,[Cu₃（OH）₂Cl₂（ina）₂]（6）,[Cu₃（OH）₂Br₂（ina）₂]（7）,[Cu₂Cl₂（ina）₂]（8）,[Cu₂Cl（ina）₂（gca）]（9）,[Cu（Me-Ina）₂]Cu₅Br₇（10） and[Me-Ina（Cu₂Br₃）]（11） have been prepared from starting materials ofcopper halide and isonicotinic aicd under solvethermal condition.The first three3D frameworks based on butterfly-like Cu₄and Cu₆clusters as SBBs show strong ferromagnetic or spin canted anti-ferromagnetic behaviors. The next two3D ferromagnetic networksbased on Cu3SBBs are generated from2D layers via Cu···X weakinteractions; With the Cu···Cl weak interactions and hydrogen bonds,the subsequent two supramolecular polymers change graduately from1D ribbons to2D layers to3D networks concerning the structurs,which present antiferromagnetic and paramagnetic couplingsrespectively; Based on the interactions of hydrogen bonds, the finaltwo SCCs constructed from1D cuprous bromide chain andisonicotinic group alkylated exhibit different luminescence, in one ofwhich there is a paddlewheel unit from copper and isonicotinic groupmethylated. From the design and syntheses of this series ofcomplexes, it is found that subtle variations of the reactionconditions such as reaction ratio, temperature, pH value, solventsand so on could lead to some regular changes of valence ststes andstructures for the final products, which make a conversion frommagnetism to luminescence at last.4. A concise conclusion was drawn and an outlook of thisresearch area was anticipated.