Syntheses, Structures And Property Studies Of Coordination Polymers Based On The Imidazole-4,5-dicarboxylic Acid Deirvative Ligands

The target of this thesis is to construct novel coordination polymers on the basis of sixdifferent kinds of imidazole-4,5-dicarboxylic acid derivative ligands（2-（pyridin-4-yl）-1H-imidazole-4,5-dicarboxylic acid,2-（4-carboxyphenyl）-1H-imidazole-4,5-dicarboxylic acid,2,4’-bi（1H-imidazole）-4,5-dicarboxylic acid,1,1’-（ethane-1,2-diyl）bis（1H-imidazole-4,5-dicarboxylic acid）,1,1’-（propane-1,3-diyl）bis（1H-imidazole-4,5-dicarboxylic acid）,1,1’-（butane-1,4-diyl）bis（1H-imidazole-4,5-dicarboxylic acid）） and d¹⁰transition metal ions aswell as lanthanide ions. The study on synthetic conditions and rules for these new compounds,topological analyses, and the exploration of relationships between structures and propertiesfor these new compounds are also carried out.Thirty-one new coordination compounds have been synthesized on the basis ofhydrothermal and solvothermal synthesis methods, and structurally characterized byelemental analyses, IR, PXRD, TG and single crystal X-ray diffractions. The thermalstabilities and fluorescent activity of these compounds have been studied.1. Eight new compounds on the basis of2-（pyridin-4-yl）-1H-imidazole-4,5-dicarboxylicacid （H₄PIDC） ligand, N-containing and carboxylate coligands with different configurationshave been hydrothermally synthesized and structurally characterized including five2D and3D complexes,[Cd₂（HPIDC）₂（bipy）]_n（1）,{[Cd₃（HPIDC）₂（btc）（H₂O）]·2H₂O}_n（2）,{[Cd₂（HPIDC）₂（bdc）_1/2（H₂O）Cl]·H₂O}_n（3）,{[Cd₂（PIDC）（Ac）（H₂O）]·H₂O}_n（4） and[Zn2（HPIDC）（ox）（H₂O）₂]n（5） constructed by transition metals, and two3D frameworks,{[Eu（HPIDC）（ox）1/2H₂O]·2H₂O}_n（6） and {[Tb（HPIDC）（ox）1/2H₂O]·2H₂O}_n（7） built bylanthanide metals. Owing to the chelating bipy ligand passivate the metal centers, socompound1only exhibits a2D layer structure formed by the inter-linking left-andright-handed helices. Compound2is a2D layer structure with the （4,4） grid topology.Compound3and4display3D （3,4）–connected and （3,4,5）–connected frameworksconstructed from ligands connecting rod-shaped SBUs. Compound5demonstrates aCd（SO4）₂network, which constructed by H₄PIDC, H₂ox and d¹⁰metal. Compound6and7areisomorphic and exhibits classical α–Po network. In addition, the luminescent properties ofthese compounds are also investigated.2. We have successfully synthesized two new ligands, namely2-（4-carboxyphenyl）-1H-imidazole-4,5-dicarboxylic acid （H₄CpIDC） and2,4’-bi（1H-imidazole）-4,5-dicarboxylic acid （H₄BIDC）. Five new compounds, [Cd₃（HCpIDC）₂（H₂O）6]n（8）,[Cd（H₂CpIDC）（H₂O）]n（9）,{[Cd₂（CpIDC）（2,2’–bpy）₂]·2H₂O}_n（10）,{[Zn3（HCpIDC）₂（4,4’–bipy）（H₂O）]·4H₂O}_n（11） and {[Zn2（CpIDC）（BIMB）]·H₂O}_n（12）were obtained by using H₄CpIDC as ligand. Four new compounds,{[Cd₂（H₂BIDC）₂（H₂O）₂]·5H₂O}_n（13）,[Cd（H₂BIDC）]n（14）,[Zn3（BIMB）₂（HBIDC）₂]n（15）and {[Cd4（BIMB）₄（H₂BIDC）₄]·6H₂O]}_n（16） were constructed by H₄BIDC ligand. Compound8is a1D zig-zag chain formed by H₄CpIDC linking CdIIions. Compound9and10exhibitsthe2D （3,3）-connected and （4,4）-connected layer structure, which built by H₄BIDC linkingbinuclear and mononuclear CdII, respectively. Compound11and12are formed fromH₄CpIDC and different linear coligands bridging ZnIIions, and they possess （4,4）-connectedand （3,4,6）-connected3D network. Compounds13and14are formed by H₄BBIDC linkingCdIIions. Different reaction solvents lead to the different structure of compounds13and14.Compound13is2D （4,4） network, while compound14displays a3D （3,3）-connectedframework. Both compound15and16constructed by H₄BBIDC and BIMB connecting d¹⁰metal centers, but different metal centers result in two different framework. They are3Dpillared （3,4）-connected and （6,6）-connected networks, respetively. Furthermore, thethermostability and luminescent properties of these compounds have been studied.3. A flexible ligand,1,1’-（ethane-1,2-diyl）bis（1H-imidazole-4,5-dicarboxylic acid）（H₄EBIDC）, was synthesized by introducing the alkyl chain between the twoimidazole-4,5-carboxylic acid groups. Five new compounds,{[Zn₄（EBIDC）₂（bbi）₃/2（H₂O）]·7H₂O}_n（17）,{[Zn₄（EBIDC）₂（bix）₂]·7H₂O}_n（18）,{[Zn₈（EBIDC）₄（bpyb）₃（H₂O）₂]·7H₂O}_n（19）,{[Zn2（EBIDC）（BIMB）]·H₂O}_n（20） and{[Zn₈（EBIDC）₄（bbi）₃]·7H₂O}_n（21） were hydrothermally synthesized based on H₄EBIDCligand, divers neutral N-containing coligands and ZnIIions. In these compounds, H₄EBIDCligands links ZnIIions generating a cage-like [Zn₄（EBIDC）₂] SBU. Different secondaryligands further connects the [Zn₄（EBIDC）₂] SBUs leading to the different structures.Compound17displays a1D ladder-like structure. Compound18possesses a3D frameworkconstructed from inter-locking1D chains. Compounds19exhibits a2D three-foldinterpenetrating （3,3）-connected net. Compound20and21are3D eight-fold interpenetratingdiamond net and non-interpenetrating （4,6）-connected net, respectively. The luminescentproperties of these compounds and ligand have been investigated.4. Two new flexible organic ligands,1,1’-（propane-1,3-diyl）bis（1H-imidazole-4,5-dicarboxylic acid）（H₄PBIDC） and1,1’-（butane-1,4-diyl）bis（1H-imidazole-4,5-dicarboxylic acid）（H₄BBIDC） were synthesizedby extending the length of the alkyl chain. We have successfully construced ten newcompounds by employing the two ligands with different coligand and metals （transition metaland lanthanide metal） under hydrothermal condition including four2D and3D complexes,[Zn（H₂PBIDC）（H₂O）]n（22）,{[Zn2（H₂PBIDC）₂（H₂O）₂]·H₂O}_n（23），[Cd（H₂PBIDC）（BIMB）]n （24） and {[Ce（HPBIDC）（H₂O）₂]·H₂O}_n（25） formed by H₄PBIDC, and six3D pillared-typecomplexes,{[Cd₃（BBIDC）3]·H₂O}_n（26）,{[Zn（BBIDC）1/2（BIMB）1/2]·H₂O}_n（27）,{[Zn（BBIDC）1/2（bix）1/2]·H₂O}_n（28）,{[Zn2（BBIDC）1/2（bytz）₂]·H₂O}_n（29）,{[Cd₂（BBIDC）1/2（bytz）₂]·3H₂O}_n（30） and {[Cd₂（BBIDC）1/2（tmpt）₂]·3H₂O}_n（31） constructedby H₄BBIDC. Both compounds22and23are formed by H₄PBIDC ligands linking ZnII, butthey exhibits two different2D layer structure. Although the assistant ligand BIMB was used,the framework of24still dispalys a2D structure. When using CeIIIas the metal centers, a3D（4,4）-connected compound25was obtained. Compound26³1are3D pillared-typecomplexes. In the framework of26, H₄BBIDC ligands with two different coordinationconfigurations can be viewed as the layer-like and pillar-like building units, respectively. Incompounds27³1, layer-like building units were built from H₄BBIDC bridging metals andthe N-containing coligands play the supporting role in the whole framework. The fluorescentstudies on those compounds based on d¹⁰metals are also discussed.