| In this thesis,eight new metal-organic coordination polymers based on the multifunctional ligands 5-amino-2,4,6-tribromoisophthalic acid(H2ATBIP)and 2-iodo-5-sulfobenzoic acid(H2isba)in combination with the N-donor flexible ligand 1,4-bis(triazole-l-methyl)benzene(bbtz)were successfully synthesized.These complexes were characterized by single crystal as well as powder X-ray diffraction analysis,infrared spectroscopy,solid-state ultraviolet-visible spectroscopy and thermogravimetric analysis.The fluorescence sensing behaviours of complexes 1-6 for metal ions,anions and nitroaromatic compounds were investigated in detail.The electrochemical properties of complexes 7 and 8 were studied.The work is introduced briefly as follows:1.Three temperature-dependent coordination polymers were obtained through the assembly between H2ATBIP,bbtz and the d10 metal ion Cd(?)at room temperature,100?and 120 ?,respectively:{[Cd(HATBIP)2(bbtz)(H2O)2]·2H2O}n(1),{[Cd(HATBIP)2(bbtz)2]·2H2O}n(2)and {[Cd3(ATBIP)2(HATBIP)2(bbtz)5]·C6H2Br4}n(3).The complex 1 presents a 3D supramolecular network with an "ABAB" stacking mode through hydrogen bonding.The Cd(?)ions in the complex 2 is hexacoordinated,exhibiting a slightly distorted octahedral geometry.Each bbtz ligand bridges the adjacent Cd(?)ions,leading to a chain.The chains are further connected by bbtz ligands to form a 2D layer.Complex 3 belongs to triclinic system with P-1 space group.The central Cdl ion is hexa-coordinated,showing slightly distorted octahedral coordination geometry.The central Cd1 and Cd2 ions are connected by bbtz ligand alternatingly in TT and GG conformations,thereby forming a necklace-like chain.In addition,these chains are further connected by ATBIP2-and bbtz ligands in mono-bidentate and TT modes,respectively,leading to the formation of a 3D framework with mesoporous channels.Complexes 1-3 show weak fluorescence properties in the solid state.Due to the polarity of the solvent,the complexes 1-3 have strong fluorescence emission in water.The fluorescence sensing properties of complexes 1-3 for Fe3+ions,Cr(?)anions and nitroaromatics(NACs)were studied in detail.2.Three coordination polymers were obtained through the assembly between H2isba,bbtz and Zn2+/Cd2+(d10)as well as Pb2+(6s2):{[Zn(bbtz)2]·2(Hisba)·5H2O}n(4),{[Cd(isba)(bbtz),.5]·H2O}n(5)and[Pb(isba)(bbtz)1.5]n(6).Complex 4 belongs to the monoclinic system with C2/c space group.The bbtz ligand with TT configuration connects the adjacent Zn(II)ions into a 1D double chain,which is composed of a 52-membered macrometalcyclic ring.These double chains are further linked by the other bbtz ligand,resulting in a 2D layer.The 2D layer is further connected into a 3D supramolecular structure by hydrogen bonding.Complex 5 belongs to the monoclinic system,P21/c space group.Cd is connected by bbtz into a staggered 1D double-stranded chain,which are further linked by bbtz to form a 2D plane.The 2D planes are joined by the isba2-anion,resulting in a 3D structure.Complex 6 belongs to the triclinic system with P-1 space group.The carboxylate group of isba2" is chelated with Pb(?),and the oxygen atom in the sulfonate group is coordinated with Pb(?)in monodentate fashion,forming a central-symmetric secondary building unit[Pb2(COO)2(SO3)2],which are connected by the isba2-ligands,resulting in a 1D double-stranded chain consisting of the alternatingly arranged 16-membered centrosymmetric macrometalcyclic rings with the dimension of 10.009 x 4.446 A2.The 1D double-stranded chains are further linked by the macrometalcyclic 14-membered ring Pb-(bbtz)2-Pb,resulting in a 2D layer.The 2D layers are further connected into a 3D framework by bbtz along the[100]direction.From topological point of view,the pseudo atoms insered in the center of[Pb2(COO)2(SO3)2]could be regarded as 6-connected nodes,and the connections between the pseudo atoms could be regarded as linkers.Therefore,the 3D framework of the complex 6 can be simplified into a 6-connected sxd network with Schlafli symbol of {33·46·55·6}.Complexes 4-6 show quantative sensing of Fe3+ions,Cr(VI)anions and NACs in the low concentration range,and may be used as fluorescent probes to these analytes.3.Two new three-dimensional complexes:{[Ni(ATBIP)(bbtz)2]·H2ATBIP}n(7)and{[Ni(ATBIP)(bbtz)(H2O)2]·3H2O}n(8)were constructed through the assembly between Ni2+and H2ATBIP in the presence of bbtz.In 7,bbtz with GG configuration and Ni(?)form a 26 membered ring(12.453 × 10.224 A2).The ring is bridged by bbtz with TT configuration to yield a 1D chain.The chain is bridged by bbtz with TT configuration to form a 2D layer.Finally,crystallographic-identical two-dimensional bbtz-bridged plans interpenetrate each other in a nearly vertical direction to form a(2D+2D?3D)three-dimensional framework.The ligand ATBIP2-further links the interpenetrating 2D layers into a 3D complete skeleton structure.In the complex 8,the two carboxylate groups of the ligand ATBIP2-bridge the Nil and Ni2 ions in monodentate fashion to form an "S"type chain,which are further connected by bbtz,generating a 3D metal-organic framework.Complexes 7 and 8 show excellent electrochemical property.Two novel enzyme-free H2O2 electrochemical sensors were constructed by post-modifying 7 and 8. |
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