【作者】 陈敏；

【导师】 孙为银；

【作者基本信息】 南京大学 ， 无机化学， 2011， 博士

【摘要】 配位聚合物不仅具有迷人的结构,而且还表现出光学、电学、磁学、吸附、分子/离子识别以及催化等性质,因此,受到了化学工作者的广泛关注,相关研究呈现出突飞猛进的发展趋势。但配位聚合物的结构受到多种因素的影响,比如温度、溶剂、抗衡离子和pH值等。因此如何通过设计有机配体、选择金属离子以及控制反应条件等实现对配位聚合物结构合理和准确的预测,成为当今的研究热点。本论文合成了一个同时含有1,2,4-三氮唑基和芳香羧酸的配体,5-(4H-1,2,4-三氮唑基)异酞酸(H2L),研究了其与不同金属盐,如Cu(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)、Mn(Ⅱ)和Ag(Ⅰ)-Ln(Ⅲ)的组装反应,并得到了24个配合物,探讨了影响配合物结构的因素,研究了相关配合物的磁学、荧光、铁电、吸附等性能。本论文主要包括以下四方面的工作：一、利用H2L配体和过渡金属盐在水热条件下反应得到8个配合物：[Cu3(μ3-OH)2(HL)4]n (1), [Co(HL)2(H2O)4]·3H2O(2), [Ni(HL)2(H2O)4]·3H2O(3), [M]n(HL)2]n(4), {[Cu2(L)2(μ-OH2)2]·3H2O}n(5),{[Co2(L)2(μ-OH2)2]·3H2O}n(6),{Ni2(L)2(μ-OH2)2]·3H2O)n(7)和{[Mn(L)(μ-OH2)]·2H20}n(8)。反应pH为4时,得到配合物1-4,其中H2L配体脱去一个羧基上的质子以HL-形式参与配位,而反应pH为7时,形成配合物5-8,脱去两个羧基上的质子以L2-形式参与配位。配合物1具有四节点(3,3,5,6)-连接的三维结构,而2和3是单核配合物,通过氢键作用连成三维超分子结构。配合物4是双节点(3,6)-连接的三维ant结构。配合物5-7是同构的,具有双节点(4,5)-连接的三维结构,而配合物8是双节点(4,6)-连接的三维结构。结果表明反应pH和金属离子对配合物的结构有重要的调控作用。磁性研究结果表明,配合物1、4、6、7和8呈现出反铁磁相互作用,而配合物5呈现出弱铁磁相互作用。二、利用H2L配体和Zn(Ⅱ)盐在不同反应条件下得到了5个配合物：{[Zn4(L)4(H2O)8]·6H2O).(9)、{[Zn2(L)2(μ-OH2)2]·3H2O)n(10).[Zn(L)(H2O)].(11). [Zn(L)(H2O)]n(12)和{[Zn10(L)8(μ3-O)2(H2O)6].8H20}n(13)。H2L配体在这5个配合物中均脱去两个羧基上的质子以L2-形式参与配位。配合物9具有二维层状结构并由氢键作用连接形成三维超分子结构。配合物10具有双结点(4,5)-连接的三维非贯穿结构。配合物11和12是同分异构体,11是一个2D+2D→2D的二重贯穿结构而12是一个三维的自贯穿msw拓扑结构。配合物13是一个具有12节点的复杂三维结构。研究结果表明反应温度和辅助配体对配合物的结构有重要的影响。研究了部分配合物的荧光和铁电性质。三、利用H2L配体和Cu(Ⅱ)盐在不同溶剂中反应得到了3个配合物：{[Cu(HL)2]·xS}n(S= DMSO和水)(14)、{(Me2NH2)2[Cu(L)2]·5.31H2O)n(15)和{[Cu3(L)2(μ2-OH)2(H20)5]·8H2O}n(16)。H2L配体在14中脱去一个羧基上的质子以HL-形式参与配位,而在15和16中脱去两个羧基上的质子以L2-形式参与配位。配合物14和15具有相似的二维(4,4)网格。配合物16具有一维孔道结构,其孔道占有率为13.1%。结果表明反应溶剂对配合物的结构有重要的影响。对配合物16吸附性质研究结果表明,16对CO2有吸附能力,对N2不吸附。四、利用H2L配体、硝酸银和稀土金属盐通过改变反应温度得到了8个4d-4f混合金属配位聚合物：{[AgLn(L)2(H2O4]}n [Ln=Nd(17),Eu(18)和Tb(19)],{[AgLn(L)2]}n[Ln=Nd(20),Eu(21)和Tb(22)]和{[AgLn(L)2(H2O)]·H2O}n[Ln=Er(23)和Yb(24)]。轻中稀土金属离子在140℃C和180℃反应分别得到结构不同的配合物,其中17-19具有二维fes拓扑结构,而20-22是双节点(4,6)-连接的三维结构。而重稀土金属离子在140℃和180 ℃反应只能得到一种结构的配合物23和24,它们具有三维三重贯穿结构。表明反应温度和金属离子对配合物结构有重要的影响。研究了部分配合物的荧光性质。更多还原

【Abstract】 Coordination polymers have attracted great attention due to their intriguing architectures as well as their potential applications in the fields of optics, ferroelectricity, magnetism, sorption, molecular/ionic recognition and catalysis. However, the structures of coordination polymers can be affected by many factors such as the reaction temperature, solvents, counter ions, pH value and so on. In order to achieve the desired complexes by rational designing organic ligands, choosing suitable metal ions and controlling reaction conditions are the research hotspots in recent years.In the dissertation, we synthesized a ligand with an amalgamation of 1,2,4-triazolyl and carboxylate groups,5-(4H/-1,2,4-triazol-4-yl)isophthalic acid (H2L), and investigated its reactions with Cu(Ⅱ), Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)、Mn(Ⅱ) and Ag(Ⅰ)-Ln(Ⅲ) salts to give 24 new complexes. The structures and properties such as magnetic, fluorescent, ferroelectric and sorption of the complexes were investigated. There are four main parts in the dissertation: 1. We successfully obtain 8 coordination complexes, [Cu3(μ3-OH)2(HL)4]n (1), [Co(HL)2(H2O)4]·3H2O (2), [Ni(HL)2(H2O)4]·3H2O (3), [Mn(HL)2]n (4), {[Cu2(L)2(μ-OH2)2]·3H2O}n (5),{[Co2(L)2(μ-OH2)2]·3H2O}n (6),{[Ni2(L)2(μ-OH2)2]-3H2O}n (7) and{[Mn(L)(μ-OH2)]-2H2O}n (8) under hydrothermal conditions. By adjusting the reaction pH, H2L ligand is partially deprotonated to give HL-form in 1-4 and completely deprotonated to afford L2- form in 5-8. The structural analysis revealed that complex 1 is a three-dimensional (3D) (3,3,5,6)-connected framework while 2 and 3 are discrete mononuclear complexes which are extended by hydrogen bonds to form 3D nets. The (3,6)-connected 3D framework of 4 is defined as a metal-organic replica of anatase (ant) net. Complexes 5-7 are isostructural and display (4,5)-connected 3D frameworks and 8 is a binodal (4,6)-connected 3D net. The results revealed that the reaction pH and the metal center play important role in determining the structures of the complexes. Magnetic studies indicate that complexes 1,4,6,7 and 8 display antiferromagnetic interactions while Complex 5 exhibits weak ferromagnetic interaction.2. Five complexes,{[Zn4(L)4(H2O)8]·6H2O}n (9),{[Zn2(L)2(μ-OH2)2]-3H2O}n (10), [Zn(L)(H2O)]n (11), [Zn(L)(H2O)]n (12) and{[Zn10(L)8(μ3-O)2(H2O)6]·8H2O}n (13), were obtained by reactions of H2L with Zn(II) salt under different reaction conditions. The H2L ligand is completely deprotonated to afford L2-form in 9-13. The structural analysis revealed that the two-dimensional (2D) layers of 9 are further linked together by hydrogen bonds to form 3D supramolecular framework while complex 10 is a (4,5)-connected 3D framework. Complexes 11 and 12 are polymorphism. Complex 11 is a two-fold interpenetrated 2D hcb network while 12 possesses rare self-penetrating msw topology. Complex 13 displays a 12-nodal 3D framework. The results show that the assembly of the complexes is greatly influenced by the reaction temperature and the auxiliary ligand. Furthermore, the photoluminescent properties of 9,11,12 and the ferroelectric property of 12 have been investigated.3. Reactions of H2L with Cu(Ⅱ) salt in different reaction solvents were carried out and 3 new complexes{[Cu(HL)2]·xS}n (S= DMSO and H2O) (14),{(Me2NH2)2[Cu(L)2]·5.31H2O}n (15) and{[Cu3(L)2C(μ2-OH)2(H2O)5]·8H2O}n (16) were obtained. The H2L ligand is partially deprotonated to give HL" form in 14 and completely deprotonated to afford L2- form in 15 and 16. Complexes 14 and 15 display similar 2D (4,4) grid networks while complex 16 has one-dimensional (1D) channel structure with 13.1% solvent accessible volume of per unit cell. The results show that the structure of the complexes is greatly influenced by the reaction solvent. The porosity of 16 was tested by gas adsorption and it exhibits adsorption for CO2 but almost no adsorption for N2.4. A series of 4d-4f heterometallic coordination complexes,{[AgLn(L)2(H2O)4]}n [Ln=Nd (17), Eu (18) and Tb (19)],{[AgLn(L)2]}n [Ln= Nd (20), Eu (21) and Tb (22)] and {[AgLn(L)2(H2O)]·H2O}n [Ln=Er (23) and Yb (24)], were obtained by reactions of H2L with lanthanide(III) nitrate, silver(I) nitrate at different temperature. By increasing the reaction temperature, the structures containing "light" and "middle" lanthanide change from 2D fes network (17-19) to 3D framework (20-22). However, reaction with the "heavy" lanthanide at both temperatures of 140 and 180℃ produces the same 3-fold interpenetrating architecture (23 and 24). The results show that the reaction temperature and the lanthanide have great influence on the structure of the complexes. Luminescent measurements revealed that 18,19,21 and 22 exhibit characteristic emission of lanthanide in the visible region with lifetime in the range of 0.24-1.81 ms.更多还原