金属氧簇基无机—有机杂化材料的研究

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英文题名：The Study of Inorganic-Organic Hybrid Materials Based on Metal-Oxygen Clusters 作者：兰亚乾 论文级别：博士 学科专业名称：物理化学 中文关键词：金属-氧簇 ; 无机-有机杂化材料 ; 晶体结构 ; 拓扑 英文关键词：metal-oxygen clusters ; inorganic-organic hybrid materials ; crystal structure ; topology 学位年度：2009 导师：苏忠民 学科代码：070304 学位授予单位：东北师范大学 论文提交日期：2009-04-01

摘要

本论文利用不同类型柔性及非中心对称的有机配体,借助配位键或分子间相互作用来剪切、修饰或桥连金属氧簇基本单元,进而构筑手性及各种新型多孔金属氧簇基无机-有机杂化化合物。研究这类化合物的合成条件和规律,以及新物质结构和性能间的关系。
     利用水热技术和常规水溶液合成方法,合成了28种新型的金属–有机配位聚合物,通过元素分析,IR,XRPD,TG和单晶X–射线衍射对晶体结构进行了表征,对化合物的热稳定性和光致发光等性质进行了初步研究。
     1、利用柔性配体bbi、钒氧笼[V_(10)O_(26)]~(4-)、不同的钒链和过渡金属Cu、Co、Ni和Zn离子在没有任何手性源的情况下构筑了一系列的多酸基手性无机-有机杂化化合物。[Cu(bbi)_2V_(10)O_(26)][Cu(bbi)]_2·H_2O (1a) [Cu(bbi)_2V_(10)O_(26)][Cu(bbi)]_2·H_2O (1b) [Ni_2(bbi)_2(H_2O)4V_4O_(12)]·2H_2O (2a) [Ni_2(bbi)_2(H_2O)4V_4O_(12)]·2H_2O (2b) [Co(bbi)(H_2O)V_2O_6] (3a) [Co(bbi)(H_2O)V_2O_6] (3b) [Zn-2(bbi)_2(V_3O_9)(OH)]·H_2O (4) [Zn_2(bbi)_2(V_4O_(12))] (5) [Zn(bbi)(V_2O_6)] (6) bbi = 1,4-bis(1H-imidazol-1-yl)butane
     非手性配体多样的构象、具有螺旋状多钒酸盐单元和笼状结构的多酸,有利于手性多酸化合物的合成。存在于分子内的弱相互作用,如氢键和Cu–O弱相互作用,在手性传递、保持和化合物的自发拆分上有很重要的作用。这些物种成功的分离不仅得到了一些迷人的结构,同时也为利用非手性配体和POM基本单元自发拆分合成手性POM基化合物提供了一种合理的方法。
     2、选用八钼酸盐,柔性配体bbi,硝酸铜,三乙胺在水热条件下调节不同pH合成了基于金属-氧簇的超分子异构体。[H_2bbi][Cu~II(bbi)_2(β-Mo_8O_(26))] (7) [Cu~II(bbi)_2(H_2O)(β-Mo_8O_(26))0.5] (8) [Cu~II(bbi)_2(α-Mo_8O_(26))][Cu~I(bbi)]_2 (9) [Cu~IICu~I(bbi)_3(α-Mo_8O_(26))][CuI(bbi)] (10) [Cu~I(bbi)]_2[Cu_2~I(bbi)_2(δ-Mo_8O_(26))_(0.5)][α-Mo_8O_(26)]_(0.5) (11) [Cu~I(bbi)][Cu~I(bbi)(θ-Mo_8O_(26))_(0.5)] (12)
     我们认为bbi配体和铜离子构筑的多样的金属-有机单元,八钼酸盐的不同构型和配位方式及多酸阴离子和金属-有机单元的非键作用对形成不同结构有重要作用。另外,随着增加有机胺的量,我们首次实现了在多酸基的金属-有机框架中将CuII不同程度的还原为CuI。有机胺不仅仅做还原剂还做缓冲溶剂降低结晶速度,有利于形成具有相似结构的化合物(如超分子异构体)。多酸基的超分子异构体的成功合成为超分子异构现象提供了新的实际模型,也有助于理解化合物结构-性质的相互关系。最重要的是这项工作将原位合成,超分子异构体,多酸化学结合起来为探索多功能材料提供新的方向。
     3、利用1,2,4-三氮唑(Hfcz)、Keggin型多酸阴离子和不同过渡金属离子构筑的八种化合物。[Zn(Hfcz)(H_2O)_3](H_3fcz)(SiMo_(12)O_(40))·3H_2O (13) [Cd_2(Hfcz)_6(H_2O)_2](SiMo_(12)O_(40))·H_2O (14) [Co_2(Hfcz)_2(SiW_(12)O_(40))](H_3fcz)_2(SiW_(12)O_(40))·10H_2O (15) [Ni_2(Hfcz)_4(H_2O)_2](SiW_(12)O_(40))·5H_2O (16) [Ag_4(Hfcz)_2(SiMo_(12)O_(40))] (17) [Cu~ICu~II(Cu~IIfcz)_2(H_2O)_5(PMo_)10_~VIMo_2~VO_(40))]·6H_2O (18) [Cu_2~I(CuIIfcz)_2(H_2O)_2(PMo_8~VIV_3~VV_3~IVO_(42))]·6H_2O (19) [Cu_4L_4PW_(12)O_(40)]·6H_2O (20) (L = 1,3-di(1H-1,2,4-triazol-1-yl)propan-2-ol)
     化合物13-17的研究结果表明氟康唑配体与不同的过渡金属构筑不同的金属有机单元,具有不同配位模式的多阴离子通过非共价的相互作用(氢键等)和共价连接金属有机单元形成了不同维数的无机-有机杂化材料。18和19是合成多酸基开放式金属-有机骨架化合物的一种可行的方法,即合并多酸阴离子和预先设计的大阳离子。多酸阴离子的大小和配位方式对化合物的孔道及最终结构有很大的影响。20中,配体氟康唑在[PW_(12)O_(40)]3-多酸阴离子、Cu2+和三乙胺存在的条件下发生的还原反应,C-C单键断裂生成的新的原位配体。在这个框架中铜阳离子作为平面正方形四连接点,Keggin多酸阴离子作为立方体八连接点。化合物20是一个新型的基于多酸的三维(4,8)连接金属有机网络。据我们所知,它代表通过共价键最高连接的多酸体系。
     4、我们设计合成了一系列柔性含氮和有机羧酸配体,利用它们和过渡金属Zn和Cd合成了八种含有过渡金属(簇)的缠结网络化合物。得到了首例(6,8)连接自穿插、(3,12)高连接、具有新的拓扑类型的八连接自穿插以及一系列既包含聚轮烷又包含聚锁烃的拓扑特性的网络结构。研究了此类化合物反应条件与产物的关系、建筑单元与拓扑结构之间的关系和新物质结构和性能之间的关系。[Zn_(2.5)L(bdc)_(2.5)]·H_2O (21) [Zn_8(μ_3-OH)_4(oba)_6(bbi)(H_2O)_2] (22) [Zn_3(bpimb)(oba)_3] (23) [Cd_2(bimb)_2(L~1)_2] (24) [Cd(bpimb)_(0.5)(L~2)(H_2O)] (25) [Zn_5(bpib)_2(L~3)_4(OH)_2(H_2O)_2] (26)[Zn(bpib)_(0.5)(L~4)] (27) [Cd(bbi)(L~4)] (28) bbi = 1,4-bis(1H-imidazol-1-yl)butane bpimb = 1,4-bis((2-(pyridin-2-yl)-1H-imidazol-1-yl)methyl)benzene bimb = 1,4-bis((1H-imidazol-1-yl)methyl)benzene bpib = 1,4-bis(2-(pyridin-2-yl)-1H-imidazol-1-yl)butane L = 1-((4'-((pyridin-3-yloxy)methyl)biphenyl-4-yl)methyl)pyridinium-3-olate H_2oba = 4,4'-oxydibenzoic acid H_2L~1 = 4-((4-(dihydroxymethyl)phenoxy)methyl)benzoic acid H_2L~2 = 4,4'-methylenebis(oxy)dibenzoic acid H_2L~3 = 3,3'-methylenebis(oxy)dibenzoic acid H_2L~4 = 4,4'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))dibenzoic acid
The aim of this thesis is the synthesis of chiral and novel porous POM based inorganic-organic hybrid compounds by using different kinds of flexible and unsymmetrical organic ligands through covalent linkage and/or molecular interaction. The study on synthetic conditions and rules for these new compounds and the exploration of relationships between structures and properties for these new compounds are also carried out.
     Twenty-eight new coordination compounds have been synthesized on the basis of hydrothermal technique and/or water solution synthesis methods and structurally characterized by elemental analyses, IR, XRPD, TG and single crystal X-ray diffractions. The thermal stabilities, fluorescent activity and et al. of these compounds have been studied.
     1. A series of chiral POM-based inorganic-organic hybrid compounds have been constructed by using the flexible bbi ligand, [V10O26]4-, [VxOy]n- chain and Cu, Co, Ni and Zn without any chiral auxiliary. [Cu(bbi)_2V_(10)O_(26)][Cu(bbi)]_2·H_2O (1a) [Cu(bbi)_2V_(10)O_(26)][Cu(bbi)]_2·H_2O (1b) [Ni_2(bbi)_2(H_2O)4V_4O_(12)]·2H_2O (2a) [Ni_2(bbi)_2(H_2O)4V_4O_(12)]·2H_2O (2b) [Co(bbi)(H_2O)V_2O_6] (3a) [Co(bbi)(H_2O)V_2O_6] (3b) [Zn-2(bbi)_2(V_3O_9)(OH)]·H_2O (4) [Zn_2(bbi)_2(V_4O_(12))] (5) [Zn(bbi)(V_2O_6)] (6) bbi = 1,4-bis(1H-imidazol-1-yl)butane
     The various conformations of achiral ligand, helical vanadate chains and polyoxometalate with cage structure, which benefit the formation of chiral polyoxometalate-based compounds. The non-covalent interactions, such as the hydrogen bond interactions and Cu–O interactions, may play crucial roles in the process of the chirality preservation and spontaneous resolution when the chirality is extended into the homochiral 3D networks. The successful isolation of these species not only produces intriguing examples of enantiomerically pure architectures but may also provide a rational strategy for synthesis of chiral POM-based compounds by using achiral ligands and POM helical units.
     2. A series of supramolecular isomers have been obtained by using (Mo8O26)4-, flexible bbi ligand, Cu(NO3)2 and Et3N at different pH values under hydrothermal conditions. [H_2bbi][Cu~II(bbi)_2(β-Mo_8O_(26))] (7) [Cu~II(bbi)_2(H_2O)(β-Mo_8O_(26))0.5] (8) [Cu~II(bbi)_2(α-Mo_8O_(26))][Cu~I(bbi)]_2 (9) [Cu~IICu~I(bbi)_3(α-Mo_8O_(26))][CuI(bbi)] (10) [Cu~I(bbi)]_2[Cu_2~I(bbi)_2(δ-Mo_8O_(26))_(0.5)][α-Mo_8O_(26)]_(0.5) (11) [Cu~I(bbi)][Cu~I(bbi)(θ-Mo_8O_(26))_(0.5)] (12)
     We believed that various copper-organic units which are formed by bbi ligands combined with CuII/CuI cations, octamolybdates with different types and coordination modes, and the nonbonding interactions between polyanions and copper-organic units are important for the formation of the different structures. With step by step increase of the amount of organic amine, we have achieved the transformation of CuII ions into CuI ones in different degrees in POMs-based MOFs for the first time. The function of organic amine may be not only as a reducer but also as a buffering agent to reduce the crystallization speed, which is in favor of forming the similar products (such as supramolecular isomers). The successful isolation of these species maybe will provide a calculable clue for the supramolecular isomerism in POMs-based MOFs, which may help to understand the structure-property relationship of POMsbased MOFs. Further research is ongoing to prepare novel supramolecular isomers and explore their valuable properties. More importantly, the combination of these three important research fields, namely, in situ synthesization, supramolecular isomerism, and polyoxometalate chemistry, opens up new possibilities in pursuit of multifunctional materials.
     3. We have designed and synthesized eight compounds based on Keggin POM, Hfcz and different transition metal under hydrothermal conditions. [Zn(Hfcz)(H_2O)_3](H_3fcz)(SiMo_(12)O_(40))·3H_2O (13) [Cd_2(Hfcz)_6(H_2O)_2](SiMo_(12)O_(40))·H_2O (14) [Co_2(Hfcz)_2(SiW_(12)O_(40))](H_3fcz)_2(SiW_(12)O_(40))·10H_2O (15) [Ni_2(Hfcz)_4(H_2O)_2](SiW_(12)O_(40))·5H_2O (16) [Ag_4(Hfcz)_2(SiMo_(12)O_(40))] (17) [Cu~ICu~II(Cu~IIfcz)_2(H_2O)_5(PMo_)10_~VIMo_2~VO_(40))]·6H_2O (18) [Cu_2~I(CuIIfcz)_2(H_2O)_2(PMo_8~VIV_3~VV_3~IVO_(42))]·6H_2O (19) [Cu_4L_4PW_(12)O_(40)]·6H_2O (20) (L = 1,3-di(1H-1,2,4-triazol-1-yl)propan-2-ol)
     The results of 13-17 indicate that differentmetal ions can form various metal–organic units and different metal–organic units, and polyanions with different coordination modes are linked to each other through non-covalent interactions and/or covalent connections to obtain different dimensionalities of compounds. For 18 and 19, we have developed a rational approach to the synthesis of POM-based open MOFs by combination of POMs and deliberately designed macrocations. Polyanions with different sizes and coordination modes have great influences on the ultimate structures of compounds. Compound 20 is a new type of (4,8)-connected 3D POM-based MOF using an in situ-generated ligand by C–C bond cleavage and reduction reaction under the presence of [PW12O40]3- polyanions, Cu2+ ions and Et3N in hydrothermal conditions, in which copper cations act as square planar four-connected nodes and Keggin polyanions act as cubical eight-connected nodes. To our knowledge, it represents the highest connected topological network via covalent linkages for the polyoxometalate systems.
     4. We have designed and synthesized a series of new N-donor and carboxylate ligands. And eight entangled net compounds with Zn or Cd metal (clusters) have been synthesized on the basis of these new ligands. An unprecedented (6,8)-connected self-penetrating network, a (3,12)-connected 3D MOF, an 8-connected self-penetrating network with the new topological type and a series of interesting topological nets showing polyrotaxane- and polycatenane-like motifs have been constructed. The study on synthetic conditions and rules for these new compounds, topological analyses, interaction of adjacent molecules, influence on the ultimate structures from ligand’s conformation and auxiliary ligand, and the exploration of relationships between structures and properties for these new compounds are also carried out. [Zn_(2.5)L(bdc)_(2.5)]·H_2O (21) [Zn_8(μ_3-OH)_4(oba)_6(bbi)(H_2O)_2] (22) [Zn_3(bpimb)(oba)_3] (23) [Cd_2(bimb)_2(L~1)_2] (24) [Cd(bpimb)_(0.5)(L~2)(H_2O)] (25) [Zn_5(bpib)_2(L~3)_4(OH)_2(H_2O)_2] (26)[Zn(bpib)_(0.5)(L~4)] (27) [Cd(bbi)(L~4)] (28) bbi = 1,4-bis(1H-imidazol-1-yl)butane bpimb = 1,4-bis((2-(pyridin-2-yl)-1H-imidazol-1-yl)methyl)benzene bimb = 1,4-bis((1H-imidazol-1-yl)methyl)benzene bpib = 1,4-bis(2-(pyridin-2-yl)-1H-imidazol-1-yl)butane L = 1-((4'-((pyridin-3-yloxy)methyl)biphenyl-4-yl)methyl)pyridinium-3-olate H2oba = 4,4'-oxydibenzoic acid H_2L~1 = 4-((4-(dihydroxymethyl)phenoxy)methyl)benzoic acid H_2L~2 = 4,4'-methylenebis(oxy)dibenzoic acid H_2L~3 = 3,3'-methylenebis(oxy)dibenzoic acid H_2L~4 = 4,4'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))dibenzoic acid

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