| Metal-organic complexes are the coordination complexes with ID,2D or 3D network structures,which are builded with organic ligands and metal ions via covalent or ionic bonds.Metal-organic complexes have become a hot research interest in the porous materials field,due to their incomparable characteristics in structural variety as well as their fundamental and industrial contributions,such as gas storage,luminescence,catalysis,separation,chirality,biotechnology,magnetism,and so forth.Design and synthesis of organic ligands is very important in the construction of metal-organic complexes.In this paper,(H6L1,H4L2 and H4L3)and(H3L4 and H6L5)were obtained through suzuki reaction and coupling reaction,respectively.Fourteen novel metal-organic complexes were obtained by the self-assemble of organic ligands and metal ions.X-ray single crystal diffraction,PXRD,IR,TGA and EA were used to characterize the structures of the complexes.Fluorescence spectra analysis,magnetic analysis,electrochemical analysis and gas adsorption analysis were used to research the potential application value.The main contents of this thesis are as follows:1.Three organic ligands were obtained through the coupling reaction,and seven metal-organic complexes were obtained through the solvothermal reaction:[Zn7(L1)2]·2NO3·8DMF·4EtOH·10H2O(1),[Cu7(L1)2·4H2O]·8DMF·5EtOH·11H2O(2),[Pr(L2)H2O]·2DMF·3.5H2O(3),[Ce2(L3)(OAc)(H2O)5]·H2O·5DMF(4),[Zn2(L3)(DMF)3]·4H2O·5.5DMF(5),[Zn2(L3)(DMA)(H2O)]·2.5H2O·3.5DMA(6),[Zn(L3)0.5(H2O)]·DMF·DMA(7).Because of the existence of inherent surface instability upon removal of solvates in zinc paddlewheel SBU,complex 1 possesses a very low surface area.Through metal-ion metathesis in a single-crystal-to-single-crystal fashion,the Zn2+ions in complex 1 were exchanged by Cu2+ions to generate complex 2.Through the measurements of gas adsorption and catalytic test,the porosity and catalytic capacity for complex 2 have been improved significantly,compared to complex 1.Complexes 3 and 4 are the Ln-complexes with different ligands.Complexes 5-7 were all 4-connected,but displayed different topological structures.Three MOFs showed interesting luminescence enhancement and quenching character for small organic molecular,the phenomenon illustrates a potential fluorescent sensor for some organic molecules and aromatic compounds.2.Three metal-organic complexes were obtained through the solvothermal reaction:[Mn3(L4)2(DMF)4(H20)]·1.5DMF·3.5H2O(8),[Cd3(L4)2(DMF)3][Cd3(L4)2(DMF)2(H2O)]·5DMF·3.5H2O(9),[Cd3(L5)(H2O)]·DMF·3H2O(10).Complex 8 and 9 display 3D open framework with(3,6)-connected and(3,3,6)-connected topology,respectively.Complex 10 exhibits a 2-nodal(5,6)-connected topology.The magnetic measurement indicates that 8 exhibits antiferromagnetic coupling interactions.Significantly,although complexes 8 and 9 have similar total solvent-accessible volumes,9 demonstrates a higher BET surface area than that of 8,further indicating the influence of the pore structure on gas absorption.3.Four coordinated architectures:[Ni(L6)(phen)(H2O)]·(H2L6)·H2O(11)[Cu(L6)(phen)(H2O)]·1.5H2O(12)[Cu2(L6)2(bipy)1.5(H2O)]·15DMF·2H2O(13)[Cd2O(L6)2(bipy)(H2O)]·2H2O·EtOH(14)were successfully obtained via hydro-or solvothermal reaction.Complex 11 and 12 are 2D coordination complexes formed via the C-H...O,C-H…Cl and C-H…Cl interactions,respectively.13 exhibits a 3D coordination polymer with a uninodal 5-connected bnn topology.Complex 14 features uninodal non-interpenetrating sql network,which is further linked into 3D structure via C…H…Cl weak interaction.Moreover,the magnetic measurements of complexes 11,12 and 13 indicate that these structures display antiferromagnetic interactions.The electrochemical measurement illustrates that 13 and 14 have the signals of the reversible redox reaction. |
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