【作者】 徐甲坤；

【导师】 毕彩丰；

【作者基本信息】 中国海洋大学 ， 海洋化学工程与技术， 2014， 博士

【摘要】 本论文综合利用含N配体与羧酸类配体与过渡金属离子在水热条件下合成21个新型配位聚合物。考察了反应条件、配体和辅助配体的几何构型、分子间作用力、氢键等因素对配位聚合物结构的影响，通过IR、元素分析、XRD和X-射线单晶衍射对晶体结构进行了表征，探究了分子自组装原理，分析了配位聚合物的网络所属的拓扑类型，并对化合物的光致发光性质和机理、热稳定性进行了初步研究。论文共分八章，主要研究内容和结论如下：第一章，主要阐述了金属有机配位聚合物的发展历程、分类、网络拓扑方法、合成方法及其应用研究，并对本论文的选题依据和目的做了总结。第二章，利用二苯甲酮-2,4’-二甲酸(H2L)作为第一配体，分别采用4,4’-联吡啶(4,4’-bipy)、1,3-二(4-吡啶)丙烷(bpp)、2-(4-吡啶)苯并咪唑(PyBIm)、1,4’-二(2-甲基咪唑)丁烷(bib)和咪唑(im)作为第二配体，用水热法设计合成了5个配位聚合物：[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和[Zn3(L)2(μ3-OH)(im)]n。其中，配合物[Ni2(L)2(4,4’-bipy)3)]·H2O]n是一个以Ni(II)离子为4连接点的{42·63·8}拓扑结构；配合物[Zn3(L)2(μ3-OH)(im)]n为{36·46·53}的拓扑结构。所得配位聚合物均具有较强的荧光活性。这一研究为半刚性二羧酸配体的研究提供一些借鉴。第三章，采用5-羟基间苯二甲酸(H2L)和1,4-二(2-甲基咪唑)丁烷(bib)用水热方法在不同的pH值下构建了两个结构不同的二元Zn(II)配位聚合物：[Zn(L)(bib)]n和[Zn(L)(bib)0.5]n。晶体结构分析结果表明，配合物[Zn(L)(bib)]n为二维层状结构，进而由分子内氢键连接形成三维结构；而配合物[Zn(L)(bib)0.5]n为六连接的三维网状结构，且两者均为pcu型拓扑结构(α-Po型拓扑)，其中配合物[Zn(L)(bib)0.5]n为二重互穿结构。这两个配位聚合物均具有较强的荧光发射，这可为定向设计特定结构的有机金属骨架提供一些借鉴。第四章，采用半刚性的有机桥连配体3,5-二(1-咪唑基)吡啶(L)作为第一配体，分别用刚性的邻苯二甲酸(H2bdc)，间苯二甲酸(H2ipa)和对苯二甲酸(H2pta)作为第二配体来满足金属离子在组装过程中的配位几何，采用水热方法合成了3个配位聚合物：[Zn4(bdc)5(L)4]n、[Cd(ipa)(L)(H2O)]n和[Co(pta)(L)]n。配位聚合物[Zn4(bdc)5(L)4]n为coo型拓扑结构，拓扑符号为{65·8}；[Cd(ipa)(L)(H2O)]n和[Co(pta)(L)]n为cds型拓扑结构，拓扑符号为{65·8}。此外，所得配位聚合物均具有一定的荧光活性。第五章，采用有机桥连配体3,5-二(1-咪唑基)吡啶和苯甲酸(Hba)作为原料，用水热方法合成了3个配位聚合物：{[Co(L)2(H2O)2]·2NO3}n、{[Mn(L)2(H2O)2]·2Cl·3H2O}n和[ZnL(ba)2]n。配合物{[Co(L)2(H2O)2]·2NO3}n和{[Mn(L)2(H2O)2]·2Cl·3H2O}n只有含N配体参与配位，均为一元配位聚合物，配合物[ZnL(ba)2]n为二元配位聚合物。配合物{[Co(L)2(H2O)2]·2NO3}n为一维链状结构，相邻的链由氢键和NO3相互连接形成三维网状结构。配合物{[Mn(L)2(H2O)2]·2Cl·3H2O}n为二维层状结构；配合物[ZnL(ba)2]n为一维zigzag链状结构，相互交联形成三维结构。此外，所得配位聚合物均具有一定的荧光活性。第六章，采用有机桥连配体3,5-二(1-咪唑基)吡啶作为第一配体，分别采用4,4’-联苯二甲酸(H2bpdc)和噻吩-2,5-二甲酸(H2tda)作为第二配体，用水热方法合成了3个Zn(II)和Cd(II)配位聚合物：[Zn(bpdc)(L)]n·2nH2O、[Zn(tda)(L)]n、和[Cd(tda)(L)(H2O)]n。配位聚合物[Zn(bpdc)(L)]n·2nH2O的拓扑结构为sql型，拓扑符号为{44}。[Zn(tda)(L)]n的拓扑结构为hcb型，拓扑符号为{63}。此外，所得配位聚合物均具有不同程度的荧光活性。第七章，采用有机桥连配体3,5-二(1-苯并咪唑基)吡啶作为第一配体，分别采用苯甲酸(Hba)、邻苯二甲酸(H2bdc)、间苯二甲酸(H2ipa)和噻吩-2,5-二甲酸(H2tda)作为第二配体，用水热方法合成了5个配位聚合物：[Cd2(ba)4(L)2]n、[Cd3(bdc)3(L)3(H2O)3]n、[Cd(ipa)(L)]n、[Zn(tda)(L)]n和[Co(tda)(L)]n。[Cd2(ba)4(L)2]n和[Cd3(bdc)3(L)3(H2O)3]n均为三连接的hcb型网络拓扑结构，拓扑符号为{63}；[Cd(ipa)(L)]n为pcu型拓扑结构，拓扑符号为{412·63}；而[Zn(tda)(L)]n和[Co(tda)(L)]n均为三连接的网状Kia型拓扑结构，拓扑符号为{82·10}。此外，所得配合物均具有不同程度的荧光活性。第八章为结论部分。本论文详细地阐述了上述21个配位聚合物的合成条件、结构特点、拓扑类型、荧光和热稳定性等性质研究等，探讨了配体类型、金属种类、反应pH对配位聚合物结构的影响，在丰富了配位聚合物合成化学和结构化学的同时，为配位聚合物的定向合成、可控组装及晶体工程理论积累了有价值的实验事实。更多还原

【Abstract】 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.更多还原