【作者】 陈海燕；

【导师】 肖冬荣；

【作者基本信息】 西南大学 ， 无机化学， 2012， 硕士

【摘要】 本论文致力于利用多种柔性长链多羧酸及咪唑、三氮唑、吡啶类氮杂环衍生物与过渡金属盐或碱土金属盐,通过水热法反应制备具有良好荧光、磁性或气体吸附性能的新型金属-有机配位聚合物。研究这类配合物的合成条件及规律,考察网络的拓扑类型及所属缠结类型,进一步探索分子自组装原理及新物质结构和性能之间的关系。利用水热技术,合成了31个由多羧酸和咪唑、三氮唑、吡啶类氮杂环衍生物配体及金属离子构筑的新型金属-有机配位网络。通过各种测试方法,如元素分析、ICP、IR、单晶X-射线衍射和粉末X-射线衍射分析(XRPD)对其晶体结构进行表征,并对它们的热稳定性(TG)、荧光或磁学特性进行了初步研究。1.利用柔性长链多羧酸与不同种类氮杂环衍生物及过渡金属盐或碱土金属盐在水热条件下反应,共合成了18种具有不同缠结类型的缠结金属-有机配位网络：[Mn4(sdba)4(bim)(H2O)4]·2H2O (1)[Ni(sdba)(bim)(H2O)2]·2H2O (2)[Co(sdba)(bim)(H2O)2]·2H2O (3)[Co3(sdba)2(Hsdba)2(2,2’-bpy)2](4)[Mn3(sdba)2(Hsdba)2(2,2’-bpy)2](5)[Mn2(sdba)2(btb)0.5(H2O)](6)[Co(sdba)(bim)](7)[Cd(sdba)(bim)](8)[Cd(sdba)(bimp)](9)[Co2(odpa)(bim)2]·3H2O (10)[Zn(sdba)(Htpim)](11)[Cd2(sdba)2(Htpim)2(H2O)2]·5H2O (12)[Mn4(μ2-OH2)2(sdba)4(bpp)4](13)[Zn2(btec)(Htpim)2]·2H2O (14)[Ba(μ2-OH2)(sdba)(btb)0.5](15)[Ni2(stba)(bim)2(H2O)]·2H2O(16)[Ni2(bpda)2(bim)2]·H2O(17)[Cd(sdba)(H2O)](18)化合物1-5代表了一系列目前缠结体系比较少见的同时具有多轮烷和多连锁特征的(2D→2D)平行互穿网络。化合物6代表了目前缠结体系第一例基于四链带的2D多连锁网络,也可以看成是由包含有[3]轮烷部件的1D多轮烷所组成。化合物7-10都是基于2D螺旋层的(2D→3D)多插指结构。化合物11是基于含侧臂1D管状结构的(1D→3D)多插指排列。化合物12是缠结体系首例基于3D自线穿网络的二重互穿结构,代表了配位聚合物领域第一例同时具有互穿和自线穿特征的配位网络。化合物13是一个包含有三折螺旋的2D自线穿网络,它代表了金属-有机配位聚合物领域中首例具有双边36-hxl (hexagonal lattice)拓扑的2D配位网络。化合物14代表了缠结体系首例基于手臂式2D双层模型的(2D→3D)多线穿网络。化合物15是金属-有机配位网络领域中第一例(5,12)-连接的3D自穿网络,代表了目前缠结体系最高连接的自穿网络。化合物16是缠结体系少见的包含有Z字链与2D螺旋层缠结的4-连接点3D自穿网络。化合物17展现出两个不同CdSO4网络的二重互穿结构。化合物18展现出两个金红石网络的双重互穿结构。2.利用4,4’-磺酰基二苯甲酸和碱土金属钡盐在不同种类有机溶剂或含氮配体存在的条件下,水热合成了7种微孔金属-有机配位聚合物：[Ba(μ2-OH2)(sdba)(H2O)3]·0.5H2O(19)[Ba(μ2-OH2)(sdba)(H2O)3]·0.5ben·H2O(20)[Ba(μ2-OH2)(sdba)(H2O)3]·0.5tolu·H2O(21)[Ba(μ2-OH2)(sdba)(H2O)3]·0.5(2,2’-bpy)·H2O(22)[Ba(μ2-OH2)(sdba)(H2O)3]·0.25bim·H2O(23)[Ba(μ2-OH2)(sdba)(H2O)3]·0.5dfb·0.25H2O(24)[Ba(μ2-OH2)(sdba)(H2O)3]·3.5H2O(25)化合物19-25是一系列包含有相同基本骨架的3D多孔配位聚合物,都是基于含侧臂2D双层模型的(2D→3D)多插指结构,只是在它们的孔道中包含有不同种类的客体分子。正是由于孔道中客体分子的不同从而导致这一系列配位化合物微观结构参数的规律性变化,如层间距、sdba配体苯环间的二面角、各孔道尺寸大小及晶体有效空腔体积等,这些微观结构参数的变化很好地展现了由客体引导的多孔配位聚合物的孔道膨胀和收缩效应,在一定程度上体现了骨架的动力学特征。此外,化合物19-25展现出强烈且有规律性的荧光发射峰变化。3.利用抗炎性药物奥沙拉嗪和线型氮杂环衍生物1,4-双(咪唑)丁烷及过渡金属盐第一次水热合成了两例基于柱形-SBU的3D柱层金属-奥沙拉嗪配位聚合物：[Co2(osa)(bim)(H2O)2](26)[Cd2(osa)(bim)(H2O)2](27)变温磁化率数据显示化合物26中CoⅡ离子之间主要表现为反铁磁性行为,而化合物27展现出良好的荧光性质。4.由有机多羧酸和芳香二齿含氮配体邻菲啰啉及过渡金属盐水热合成了4种金属-有机配位超分子网络：[Cd(bqdc)(phen)](28)[Cd2(bctc)(phen)2(H2O)]·3H2O (29)[Mn2(cptc)(phen)3]·4.5H2O (30)[Zn(H2btc)(phen)2]+-H2btc-·3.5H2O (31)化合物28是由包含有meso-螺旋的2D(4,4)网络通过phen芳香环间的π-π堆积及C-H…O氢键作用连接形成的3D超分子网络。化合物29是由包含有四边形[Cd4(bctc)4(phen)4]建筑单元的2D网络进一步通过phen芳香环间的π-π堆积作用形成的3D超分子网络。化合物30和31仅表现出组分分别为[Mn4(cptc)2(phen)6]和[Zn2(H2btc)2(phen)4]2+的零维结构,这些零维组分与游离分子一起在三维空间平行排列形成3D超分子网络。更多还原

【Abstract】 The aim of this thesis is to synthesize novel metal-organic coordination polymers which perhaps exhibit well photoluminescence, magnetic or gas adsorption/desorption properties, on the basis of flexible long-chain polycarboxylate, diverse N-heterocyclic derivatives of imidazole, triazol, or pyridyl ligands, and transition metal salts or alkaline-earth metal salts by hydrothermal techniques, to study the synthetic conditions and rules for these compounds, to analysize the topological types and entangled types, and to further explore the principle of self-assembley as well as the relationships between structures and properties for these new compounds.Thirty-one new metal-organic coordination polymers have been synthesized by hydrothermal reactions of polycarboxylate and metal ions in the presence of diverse N-heterocyclic derivatives of imidazole, triazol, or pyridyl ligands. Their structures were characterized by elemental analyses, ICP analyses, IR spectra, single-crystal X-ray diffraction analyses and X-ray powder diffraction (XRPD); while the thermal stabilities (TG), fluorescent and/or magnetic properties of these compounds have also been studied.1. Eighteen new metal-organic coordination networks with different types of entanglement have been hydrothermally synthesized by self-assembly of flexible long-chain polycarboxylate and transition metal salts or alkaline-earth metal salts in the presence of different N-heterocyclic derivatives, that are,[Mn4(sdba)4(bim)(H2O)4]-2H2O (1)[Ni(sdba)(bim)(H2O)2]-2H2O (2)[Co(sdba)(bim)(H2O)2]-2H2O (3)[Co3(sdba)2(Hsdba)2(2,2’-bpy)2](4) [Mn3(sdba)2(Hsdba)2(2,2’-bpy)2](5)[Mn2(sdba)2(btb)o.5(H20)](6)[Co(sdba)(bim)](7)[Cd(sdba)(bim)](8)[Cd(sdba)(bimp)](9)[Co2(odpa)(bim)2]-3H2O (10)[Zn(sdba)(Htpim)](11)[Cd2(sdba)2(Htpim)2(H2O)2]-5H2O (12)[Mn4(μ2-OH2)2(sdba)4(bpp)4](13)[Zn2(btec)(Htpim)2]·2H2O (14)[Ba(μ2-OH2)(sdba)(btb)0.5](15)[Ni2(stba)(bim)2(H2O)]·2H2O (16)[Ni2(bpda)2(bim)2]·H2O (17)[Cd(sdba)(H2O)](18)Compounds1-5are all uncommon (2D→2D) parallel interpenetrating arrays with coexistence of polyrotaxane and polycatenane, which are still quite rare in entangled systems up to now. Compound6represents the first example of2D polycatenated framework formed by1D quadruple chains, which could equally well be considered as formed by interconnected1D polyrotaxane columns involving unusual [3]rotaxane components. All of compounds7-10exhibit (2D→3D) interdigitated architectures assembled from different2D layers with helical structures. Compound11exhibits a novel (1D→3D) interdigitated architecture that is obtained from the self-assembly of1D tubelike structures. Compound12is the first case of interpenetration of two identical3D self-threading frameworks for entangled syatems, which represents the first entangled coordination polymer containing both interpenetration and self-threading feature. Compound13is a peculiar2D self-threading network containing unusual triflexural helical motifs, which can be rationalized as a6-connected2D36-hxl (hexagonal lattice) net with double edges. Compound14displays a new (2D→3D) polythreaded network that is obtained for the first time from the self-assembly from2D bilayer frameworks with dangling lateral arms. Compound15defines a new self-penetrating topology for binodal (5,12)-connected3D network, and represents the highest connected topology presently known for self-penetrating system. Compound16is a new4-connected3D self-penetrating network containing unusual entangled motifs, which are the interlock of Z-shaped chains and2D layers with helical structures. Compound17represents an unusual mode of interpenetration of two distinct3D frames both with CdSO4topology. Compound18exhibits an unusual twofold interpenetrating array with (3,6)-connected rutile topology.2. Seven porous metal-organic coordination polymers have been prepared by self-assembly of4,4’-sulfonyldibenzoic acid and alkaline-earth barium(II) ions in the presence of organic solvent molecules or assistant N-containing ligands, that are,[Ba(μ2-OH2)(sdba)(H2O)3]0.5H2O (19)[Ba(μ2-OH2)(sdba)(H2O)3]0.5ben-H2O (20)[Ba(μ2-OH2)(sdba)(H2O)3]0.5tolu-H2O (21)[Ba(μ2-OH2)(sdba)(H2O)3]-0.5(2,2’-bpy)-H2O (22)[Ba(μ2-OH2)(sdba)(H2O)3]-0.25bim-H2O (23)[Ba(μ2-OH2)(sdba)(H2O)3]0.5dfb-0.25H2O (24)[Ba(μ2-OH2)(sdba)(H2O)3]-3.5H2O (25)Compounds19-25are a series of3D porous coordination polymers exhibitting the same (2D→3D) interdigitated arrays assembled from unusual sidearm-containing2D bilayer motifs, which possess similar interlayer channels but encapsulate various species of guest molecules. These compounds show a series of variable parameters associated with the change of the species of guest molecules in their channels, including interlayer distance, dihedral angle of phenyl groups of sdba, dimension of channels and effective free volume, which well indicate the effect of guest-induced expanding and shrinking porous modulationm, and give a clue to a dynamic arrangement in this system. Furthermore, compounds19-25exhibits a series of intense and regular change of the luminescence behaviors.3. Two three-dimensional (3D) pillared metal-olsalazine complexes based on infinite rod-shaped secondary building units (SBUs) have been firstly isolated by hydrothermal reactions of anti-inflammatory drug olsalazine with a linear N-heterocyclic derivative1,4-bis(imidazol-l-yl)butane and transition metal salts, that are,[Co2(osa)(bim)(H2O)2](26)[Cd2(osa)(bim)(H2O)2](27)The variable-temperature magnetic data of compound26indicate a strong antiferromagnetic interaction between the CoⅡ ions. However, compound27displays good luminescent property.4. Four new metal-organic coordination supramolecular networks have been hydrothermally synthesized by using aromatic bidentate chelating ligand 1,10-phenanthroline with different polycarboxylate and transition metal salts, that are,[Cd(bqdc)(phen)](28)[Cd2(bctc)(phen)2(H2O)]·3H2O (29)[Mn2(cptc)(phen)3]-4.5H2O (30)[Zn(H2btc)(phen)2]+-H2btc-·3.5H2O (31)Compound28is comprised of2D(4,4) layers containning meso-helix motifs, which further connected by aromatic π-π stacking and C-H···O hydrogen-bonding interactions to form a3D supramolecular network. Compound29is composed of2D layers obtained by extending of quadrangle building blocks [Cd4(bctc)4(phen)4], which further connected by aromatic π-π stacking interactions to form a3D supramolecular network. Both compounds30and31exhibit0D structures of composition [Mn4(cptc)2(phen)6] and [Zn2(H2btc)2(phen)4]2+, respectively, which are further arranged with free molecules in spatial space to form3D supramolecular networks.更多还原