【作者】 杨嫣；

【导师】 马建方；

【作者基本信息】 东北师范大学 ， 无机化学， 2014， 博士

【摘要】 本论文以芳香羧酸和柔性含氮配体与过渡金属离子在水热条件下自组装合成了一系列配位聚合物。我们采用X射线单晶衍射技术确定这些化合物的结构，并用元素分析、红外光谱(IR)、X射线粉末衍射(PXRD)及热重分析(TGA)技术进一步对其进行表征；探索这类化合物的合成条件；从拓扑学的角度着手研究化合物的晶体结构；考察有机配体的结构特点对产物结构的影响。此外，对一些化合物的发光及漫反射光谱做了初步研究。1.利用8种结构相关的水杨酸类配体(H2L1=salicylic acid、H2L2=3-methylsalicylic acid、H2L3=4-methylsalicylic acid、H2L4=4-chlorosalicylic acid、H2L5=5-chlorosalicylic acid、H2L6=5-bromosalicylic acid、H2L7=5-nitrosalicylicacid和H3L8=5-sulfosalicylic acid)和柔性含氮配体1,1’-(1,4-butanediyl)bis(imidazole)(biim-4)与Zn(II)和Cd(II)在水热条件下合成了13个配合物：[Zn2(L1)2(biim-4)(H2O)](1)、[Cd(HL1)2(biim-4)](2)、[Cd(HL2)2(biim-4)](3)、[Cd(HL3)2(biim-4)](4)、[Zn2(L4)2(biim-4)(H2O)](5)、[Cd(HL4)2(biim-4)](6)、[Zn2(L5)2(biim-4)(H2O)](7)、[Cd2(HL5)4(biim-4)3]2H2O(8)、[Zn2(L6)2(biim-4)(H2O)](9)、[Cd(HL6)2(biim-4)](10)、[Zn2(L7)2(biim-4)2]·H2O(11)、[Cd2(L7)2(biim-4)2(H2O)]·H2O (12)和[Zn(HL8)(biim-4)]·0.5H2O (13)。化合物1和5是同构的，展示了相同的三维3-连接的103-ths网络。化合物2具有一维内消旋链状结构。化合物3呈现零维二聚体结构，该结构进而被π-π堆积扩展为二维超分子层。化合物4和6具有相似的1D链。这些链进而被化合物中的C–H···O和C–H···Cl氢键扩展为二维超分子层。化合物7和9是同构的，为典型的三维diamond网络。化合物8呈现2D→3D多聚穿套结构。化合物10呈现了一个由C–H···Br氢键形成的二维44-sql超分子层。化合物11和12具有双节点(4,4)-连接的三维(4·53·72)(4·52·83)和(42·62·82)(42·6·82·10)拓扑。化合物13为三维四重互穿的diamond网络。重点讨论了有机阴离子和中心金属离子对产物结构的影响。此外，我们对这些化合物的发光行为做了初步研究。2.选用3,5-二硝基水杨酸(H2dns)和九种结构相关的柔性双三氮唑配体(L1=1,2-bis(1,2,4-triazol-1-yl)ethane、 L2=1,3-bis(1,2,4-triazol-1-yl)propane、 L3=1,4-bis(1,2,4-triazol-1-yl)butane、 L4=1,5-bis(1,2,4-triazol-1-yl)pentane、 L5=1,5-bis(1,3,4-triazol-1-yl)pentane、 L6=1,6-bis(1,2,4-triazol-1-yl)hexane、 L7=1,10-bis(1,2,4-triazol-1-yl)decan、L8=1,4-bis((1H-1,2,4-triazol-1-yl)methyl)benzene和L9=1,1’-(2,2’-oxybis(ethane-2,1-diyl))bis(1H-1,2,4-triazole))与Cu(II)和Cd(II)在水热条件下合成了11个配合物：[Cu4(dns)4(L1)2(H2O)]·2H2O (14)、[Cu4(dns)4(L2)2(H2O)](15)、[Cu2(dns)2(L3)(H2O)](16)、[Cu2(dns)2(L4)(H2O)](17)、[Cu5(dns)4(OH)2(L5)2(H2O)3]·H2O (18)、[Cu(dns)(L6)](19)、[Cu2(dns)2(L7)](20)、[Cu(dns)(L8)]·0.5H2O (21)、[Cd2(dns)2(L1)(H2O)2](22)、[Cd2(dns)2(L7)3](23)和[Cd4(dns)4(L9)4](24)。化合物14和17为一维双链结构。化合物15、16和18为二维44网格。化合物19展示了一个三维单节点8-连接的自穿(42068)网络。化合物20具有二维两重互穿的44-sql网格。化合物21和22为二维波浪状层。化合物23为一维链状结构。化合物24具有零维四核簇结构。重点讨论了双三氮唑配体对化合物结构的影响。此外，我们对室温下化合物的漫反射光谱做了初步研究。3.以芳香多羧酸(o-H2BDC=phthalic acid、m-H2BDC=isophthalic acid、p-H2BDC=terephthalic acid和H4BTEC=pyromellitic acid)和三种4-取代双(1,2,4-三氮唑)配体(L10=1,2-bis(2-(4H-1,2,4-triazol-4-yl)phenoxy)ethane、 L11=1,2-bis(3-(4H-1,2,4-triazol-4-yl)phenoxy)ethane和L12=1,2-bis(4-(4H-1,2,4-triazol-4-yl)phenoxy)ethane)与Zn(II)和Cd(II)在水热条件下反应得到11个配合物：[Zn(L1)(o-BDC)]·1.5H2O (25)、[Zn(L1)(m-BDC)](26)、[Cd2(L1)(BTEC)]·H2O (27)、[Zn(L2)(m-BDC)]·1.25H2O (28)、[Zn(L2)(p-BDC)]·4H2O (29)、[Cd(L2)(p-BDC)]·H2O (30)、[Zn2(L2)(BTEC)](31)、[Zn(L3)(m-BDC)]·3.5H2O (32)、[Zn2(L3)(p-BDC)2]·2H2O (33)、[Zn2(L3)2(BTEC)]·2H2O (34)和[Cd2(L3)2(BTEC)](35)。化合物25为二维层状结构。化合物26具有一维链状结构，该链进而被π π堆积扩展为二维超分子层。化合物27展示了三维(4,8)-连接的(32·42·52)(34·48·512·64)网络。化合物28包含两个互锁的单壁金属-有机纳米管(single-wall metal-organic nanotube, SWMONTs)，该结构兼具多聚轮烷和多聚索烃的特征。化合物29为三维五重互穿的diamond网络。化合物30为三维α-Po网络。化合物31为三维(4,6)-连接的(43·63)(46·66·83)网络。化合物32为二维4-连接的(65·8)网格。化合物33为三维三重互穿的α-Po网络。化合物34和35展示了相同的三维(4,4)-连接的(64·7·8)(62·84)网络。着重讨论了4-取代双(1,2,4-三氮唑)配体、芳香多羧酸阴离子和金属离子对自组装过程的影响。此外，我们还研究了室温下化合物25-35的发光行为和化合物2831在不同溶剂中的悬浊液的荧光性质。更多还原

【Abstract】 In this work, a series of coordination polymers (CPs) constructed from aromaticcarboxylic acids, flexible N-donor ligands and transition metal ions have beensynthesized under hydrothermal conditions and characterized by the single crystalX-ray diffraction, elemental analyses, infrared spectra (IR), powder X-ray diffractionspectra (PXRD) and thermogravimetric analysis (TGA). The synthesis conditions,topologies of crystal structures, influences of structural features of organic ligands onthe structures of final products have been investigated in detail. In addition, theluminescent properties and diffuse reflectivity spectra have also been studiedpreliminarily.1. Eight structurally related salicylate ligands (H2L1=salicylic acid, H2L2=3-methylsalicylic acid, H2L3=4-methylsalicylic acid, H2L4=4-chlorosalicylic acid,H2L5=5-chlorosalicylic acid, H2L6=5-bromosalicylic acid, H2L7=5-nitrosalicylicacid and H3L8=5-sulfosalicylic acid) and the flexible N-donor ligand (biim-4=1,1’-(1,4-butanediyl)bis(imidazole)) were used as organic ligands, and thirteen newZn(II)/Cd(II)-containing complexes, namely,[Zn2(L1)2(biim-4)(H2O)](1),[Cd(HL1)2(biim-4)](2),[Cd(HL2)2(biim-4)](3),[Cd(HL3)2(biim-4)](4),[Zn2(L4)2(biim-4)(H2O)](5),[Cd(HL4)2(biim-4)](6),[Zn2(L5)2(biim-4)(H2O)](7),[Cd2(HL5)4(biim-4)3]2H2O (8),[Zn2(L6)2(biim-4)(H2O)](9),[Cd(HL6)2(biim-4)](10),[Zn2(L7)2(biim-4)2]·H2O (11),[Cd2(L7)2(biim-4)2(H2O)]·H2O (12), and[Zn(HL8)(biim-4)]·0.5H2O (13), have been synthesized under hydrothermalconditions. Compounds1and5are isomorphous, and show the same3-connected103-ths net. Compound2possesses a meso-helical chain structure. Compound3shows a zero-dimensional (0D) dimeric molecular structure, which is linked by π–πinteractions into a two-dimensional (2D) supramolecular assembly. Compounds4and6exhibit similar one-dimensional (1D) chains, which are extended into different2Dsupramolecular layers via C–H···O and C–H···Cl hydrogen-bonding interactions,respectively. Compound9is isomorphous with7, and displays a typicalthree-dimensional (3D) diamond framework. Compound8shows an unusual2D→3Dpolythreading array. Compound10furnishes a2D supramolecular44-sql networkformed by C–H···Br hydrogen-bonding interactions. Compounds11and12exhibitbinodal (4,4)-connected3D frameworks with (4·53·72)(4·52·83) and(42·62·82)(42·6·82·10) topologies, respectively. Compound13has a3D4-fold interpenetrating diamond framework. The effects of the organic anions and centralmetal ions on the structures of products have been discussed in detail. Moreover, theluminescent behaviors of1-13have also been investigated.2. The combination of3,5-dinitrosalicylic acid (H2dns) and nine flexiblebis(triazole) ligands (L1=1,2-bis(1,2,4-triazol-1-yl)ethane, L2=1,3-bis(1,2,4-triazol-1-yl)propane, L3=1,4-bis(1,2,4-triazol-1-yl)butane, L4=1,5-bis(1,2,4-triazol-1-yl)pentane, L5=1,5-bis(1,3,4-triazol-1-yl)pentane, L6=1,6-bis(1,2,4-triazol-1-yl)hexane, L7=1,10-bis(1,2,4-triazol-1-yl)decane, L8=1,4-bis((1H-1,2,4-triazol-1-yl)methyl)benzene and L9=1,1’-(2,2’-oxybis(ethane-2,1-diyl))bis(1H-1,2,4-triazole)) in the presence of Cu(II) andCd(II) ions provides eleven complexes, which are formulated as[Cu4(dns)4(L1)2(H2O)]·2H2O (14),[Cu4(dns)4(L2)2(H2O)](15),[Cu2(dns)2(L3)(H2O)](16),[Cu2(dns)2(L4)(H2O)](17),[Cu5(dns)4(OH)2(L5)2(H2O)3]·H2O (18),[Cu(dns)(L6)](19),[Cu2(dns)2(L7)](20),[Cu(dns)(L8)]·0.5H2O (21),[Cd2(dns)2(L1)(H2O)2](22),[Cd2(dns)2(L7)3](23) and [Cd4(dns)4(L9)4](24).Compounds14and17possess one-dimensional (1D) double chains. Compounds15,16and18show2D44networks. Compound19furnishes a3D uninodaleight-connected self-penetrating framework with (42068) topology. Compound20reveals a2D2-fold interpenetrating44-sql network. Compounds21and22feature2Dundulated layers. Compound23shows a1D chain. Compound24furnishes a discretetetranuclear cluster. The influence of the bis(triazole) ligands on the structures ofcompounds are discussed in detail. Furthermore, the diffuse reflectivity spectra ofcompounds have also been studied at room temperature.3. Eleven Zn(II)/Cd(II)-containing coordination polymers incorporating bothflexible4-substituted bis(1,2,4-triazole) ligands (L10=1,2-bis(2-(4H-1,2,4-triazol-4-yl)phenoxy)ethane, L11=1,2-bis(3-(4H-1,2,4-triazol-4-yl)phenoxy)ethane and L12=1,2-bis(4-(4H-1,2,4-triazol-4-yl)phenoxy)ethane) and polycarboxylate anions(o-H2BDC=phthalic acid, m-H2BDC=isophthalic acid, p-H2BDC=terephthalicacid, and H4BTEC=pyromellitic acid), namely,[Zn(L1)(o-BDC)]·1.5H2O (25),[Zn(L1)(m-BDC)](26),[Cd2(L1)(BTEC)]·H2O (27),[Zn(L2)(m-BDC)]·1.25H2O (28),[Zn(L2)(p-BDC)]·4H2O (29),[Cd(L2)(p-BDC)]·H2O (30),[Zn2(L2)(BTEC)](31),[Zn(L3)(m-BDC)]·3.5H2O (32),[Zn2(L3)(p-BDC)2]·2H2O (33),[Zn2(L3)2(BTEC)]·2H2O (34) and [Cd2(L3)2(BTEC)](35), have been prepared andidentified by physical measurements. Compound25possesses a layered structure.Compound26shows1D chains. Weak π-π intermolecular stackings further join thesechains into a2D supramolecular layered structure. Compound27displays a3D(4,8)-connected (32·42·52)(34·48·512·64) net. Compound28consists of two interlocked single-wall metal-organic nanotubes (SWMONTs) with both polyrotaxane andpolycatenane characters. Compound29exhibits a3D5-fold interpenetrating diamondmotif. Compound30furnishes a3D α-Po net. Compound31reveals a3D(4,6)-connected net with (43·63)(46·66·83) topology. Compound32features a2D4-connected network with (65·8) topology. Compound33shows a3D3-foldinterpenetrating α-Po net. Compounds34and35display3D (4,4)-connected nets withthe same (64·7·8)(62·84) topology. The effects of the4-substituted bis(1,2,4-triazole)ligands, aromatic polycarboxylate anions, and metals ions on the frameworkassemblies have been discussed. Besides, the solid-state luminescent of compounds25-35and fluorescent properties of compounds2831in various solvent suspensionswere investigated at room temperature.更多还原