Studies On The Synthsis, Structures And Properties Of Transition Metal Coordination Polymers Based On N-containing And Carboxylate Ligands

In this study,21new coordination polymers were synthesized by comprehensiveutilization of N-containing ligands, carboxylic acid ligands and transition metal ionsunder hydrothermal conditions. The influence of reaction conditions, geometricstructure of coordination ligands, intermolecular force, hydrogen bond on thestructure of coordination polymers were studied. Meanwhile, the structures ofcoordination polymers were characterized by IR, elemental analysis, XRD and X-raydiffraction analysis. The self-assembly principles of these coordination polymers wereinvestigated and the topology analysis were carried out to understand the structures ofcoordination polymers more clearly. Furthermore, the thermogravimetric analyseswere carried out to study the thermal stability of the compounds, whilephotoluminescence properties were also investigated in the solid state at roomtemperature.The thesis includes eight chapters, and the main contents and conclusions are asfollows:Chapter1maily focuses on the development history, classification of metal-organic coordination polymers, the network topology methods, the synthesis andapplications of metal-organic coordination polymers, the basis and purpose of thisresearch.In chapter2, five new coordination polymers, namely,[Ni2(L)2(4,4’-bipy)3)]·H2O]n,[Ni2(L)2(O)(bpp)2]n,[Zn(L)(bib)0.5]n,[Zn(L)(PyBIm)]n, and[Zn3(L)2(OH)(im)]n[H2L=benzophenone-2,4’-dicarboxylic acid,4,4’-bipy=4,4’-bipyridine, bpp=1,3-bis(4-pyridyl)propane, PyBIm=2-(4-pyridyl) benzimidazole, and im=imidazole] were synthesized under hydrothermal conditions.Structure determination revealed that [Ni2(L)2(4,4’-bipy)3)]·H2O]nis a3D networkand exhibits a4-connected metal-organic framework with {42·63·8} topology.[Zn3(L)2(OH)(im)]npossesses a6-connected node with the Schl fli symbol of{36·46·53}. All the obtained coordination polymers demonstrate good luminescentproperties.In chapter3, two new coordination polymers [Zn(L)(bib)]nand [Zn(L)(bib)0.5]n[L=5-hydroxyisophthalic acid and bib=1,4-bis(2-methyl-imidazol-1-yl)butane] havebeen synthesized and characterized. The structural analysis indicates that[Zn(L)(bib)]nis a2D layered structure, which are further assembled into a3Dsupramolecular structure by intermolecular hydrogen bonding;[Zn(L)(bib)0.5]npossesses a3D6-connected net. Both of them exhibit pcu topology, wheras[Zn(L)(bib)0.5]nfeatures a two-fold interpenetrated structure. Moreover, both of themhave luminescent properties.In chapter4, three coordination polymers [Zn4(bdc)5(bip)4]n,[Cd(ipa)(bip)(H2O)]nand [Co(pta)(bip)]n[bip=3,5-bis(imidazole-1-yl)pyridine, H2bdc=1,2-benzene dicarboxylate acid, H2ipa=isophthalic acid, H2pta=terephthalic acid]were synthesized and characterized.[Zn4(bdc)5(bip)4]npossesses coo type topologywith a symbol of {65·8}, while both of [Cd(ipa)(bip)(H2O)]nand [Co(pta)(bip)]ntakecds type topology with a symbol of {65·8}. All of the three coordination polymershave luminescent properties.In chapter5, three metal coordination polymers {[Co(L)2(H2O)2]·2NO3}n,{[Mn(L)2(H2O)2]·2Cl·3H2O}nand [Zn(L)(ba)2]n[bip=3,5-bis(imidazole-1-yl)pyridine, Hba=benzoic acid] were synthesized and structurally characterized.{[Co(L)2(H2O)2]·2NO3}nshows a1D chain structure, and the adjacent chains areconnected by hydrogen bonding and nitrate groups to form a3D network.{[Mn(L)2(H2O)2]·2Cl·3H2O}nfeatures a2D layer structure. A3D network isconstructed through the cluster consisting of two chloride ions and three watermolecules.[Zn(L)(ba)2]nshows a1D zigzag chain structure that further twiststogether to form a3D network. Moreover, all these three coordination polymers show good luminescent properties.In chapter6, three metal coordination polymers [Zn(bpdc)(bip)]n·2nH2O,[Zn(tda)(bip)]nand [Cd(tda)(bip)]n[bip=3,5-bis (imidazole-1-yl)pyridine, H2bpdc=biphenyl-4,4’-dicarboxylate, H2tda=thiophene-2,5-dicarboxylate] were synthesizedunder hydrothermal conditions by employing N-containing ligand L and the auxiliarycarboxylic acids.[Zn(bpdc)(bip)]n·2nH2O possesses sql type topology with a symbolof {44}, while [Zn(tda)(bip)]nshowes hcb type topology with a symbol of {63}. Inaddition, both of the two coordination polymers show good luminescent properties.In chapter7, five metal coordination polymers [Cd2(ba)4(L)2]n,[Cd3(bdc)3(L)3(H2O)3]n,[Cd(ipa)(L)]n,[Zn(tda)(L)]nand [Co(tda)(L)]n[Hba=benzoic acid, H2bdc=1,2-benzene dicarboxylate acid, H2ipa=isophthalic acid,H2tda=thiophene-2,5-dicarboxylate] were synthesized under hydrothermalconditions.[Cd2(ba)4(L)2]n,[Cd3(bdc)3(L)3(H2O)3]npossess3-connected hcb typetopology with a symbol of {63};[Cd(ipa)(L)]nshowes pcu type type topology with asymbol of {412·63}；Both of [Zn(tda)(L)]nand [Co(tda)(L)]ngive rise to uniform3-connected kia type nets with Point (Schl fli) symbol of {82·10}. The TG analysisindicate coordination polymers [Zn(tda)(L)]nand [Co(tda)(L)]nare stable up to400℃. Moreover, all of these five complexes show luminescent properties.Chapter8is the conclusion.This thesis describes in detail the synthesis, structural characteristics, topology,luminescent property and thermostability of the above21coordination polymers.Meanwhile, the influence of ligands, metal ions and pH value on the coordinationpolymer structure and topology were explored. This research not only enriches thesynthesis and structural diversity of coordination polymers, but also accumulatesvaluable experimental facts for the oriented synthesis, controllable assembly and thecrystal engineering theory of coordination polymers.