【作者】 邵奎占；

【导师】 王荣顺； 苏忠民；

【作者基本信息】 东北师范大学 ， 物理化学， 2008， 博士

【摘要】 金属—有机配位聚合物作为一种新型的分子功能材料,凭借其独特的结构可剪裁性、多样的拓扑结构和在氢气存储、离子交换、吸附、分子识别、催化以及光、电、磁、手性拆分等领域的巨大潜在应用受到了各界科学家们越来越多的关注。依据分子工程学原理,通过选择特定几何构型的中心金属离子和特殊的有机配体,可以在一定程度上实现新型功能材料的定向设计和合成。同时,还可以通过选择功能性的中心金属离子和具有功能官能团的有机配体赋予目标化合物以多功能的性质。本论文选择不同构型的有机配体和金属离子合成出21种金属—有机配位聚合物。研究这些化合物的合成条件及规律,分析网络结构所属的拓扑类型,考察配体的几何构型,辅助配体对于整个结构的影响等规律,探究分子自组装原理。对化合物的热稳定性、荧光性质和压电性质进行了初步研究。这些研究结果主要包括以下五个方面:1、合成了新颖的含氮螯合配体—4,5-二氮杂芴-9-肟（L1）,与不同构型的共配体和过渡金属在水热条件下反应,成功得到了四个三维的金属有机框架化合物:[Zn₂（BOABA）（L1）（OH）]·2H₂O（1） , [Zn₂（BOABA）（L1）（OH）]·4H₂O（2） ,[Zn₃（TMA）₂（OH）]·[N（C₄H₉）₄]（3）,[Cu₂（BTEC）（OH）]·（L1）（4）。化合物1中,在螯合配体作用下,椅式构型的四核锌与三齿的BOABA羧酸配体相连接,构成了3,6-连接的金红石网络结构。化合物2中,在螯合配体作用下,船式构型四核锌与三齿的BOABA羧酸配体相连接,构成了新颖的3,6-连接拓扑网络（4.6²）.（4².6⁹.8⁴）。以配体L1作为结构导向剂,在化合物3中通过三核锌簇和TMA的连接构筑了具有（4.6²） （6³） (4.6¹¹.8³)拓扑结构的新颖3,6-连接金属有机框架结构。化合物4是由四核铜簇与均苯四甲酸配体连接构成的4,8-连接的scu拓扑网络结构。2、利用新颖的4,5-二氮杂芴-9-肟氧-3-吡啶（L2）,共配体和过渡金属在水热条件下,得到了四个不同结构的配位聚合物:[Cd（BDC）（L2）]（5）,[Cd₂（bpdc）₂（L2）₂]（6）,[Cd（oba）（L2）]·H₂oba（7）,[Cd（BTEC）_0.5（L2）]·（H₂O）（8）。化合物5和6中,5-二氮杂-9-肟氧-3-甲基吡啶与金属镉原子构成了一个环状的[CdL2]2构筑单元,进一步通过直线型羧酸的连接构成（6,3）二维平面结构。化合物5通过（6,3）二维平面的倾斜互穿构成了三维的超分子网络结构。化合物6中两个平行的二维层通过平行连锁形成了二维双层结构,二维双层结构通过倾斜互穿构成了新颖的三维超分子网络结构。化合物7中,配体4,5-二氮杂-9-肟氧-3-甲基吡啶和oba配体都是以折线形桥连的方式与金属镉配位,形成了由左、右手螺旋链支撑构筑的含有一维纳米孔道的二维层状结构。在化合物8中通过环状的[CdL2]2构筑单元和均苯四甲酸配体的连接构成了新颖的3,4-连接的三维网络结构。3、利用新颖的4,5-二氮杂芴-9-肟氧乙酸（L3）,共配体和过渡金属在水热反应条件下,得到了五个不同结构的配位聚合物:[Zn₂（BDC）_1.5（L3）]·H₂O（9）,[Zn₂（BDC）_0.5（m-BDC） （L3）（H₂O）]·H₂O（10）,[Zn₄（m-BDC）₄（L3）₂（OH）₂]·3H₂O（11）,[Zn₂（BTC）（L3）（H₂O）]·H₂O（12）,[Zn₃（TMA） （L3）₂（OH）]·2H₂O（13）。化合物9是由4,5-二氮杂芴-9-肟氧乙酸和对苯二甲酸构成的以双核锌为5节点的新颖5连接三维网络结构。化合物10-12是4,5-二氮杂芴-9-肟氧乙酸和芳香羧酸构成的不同的二维层状结构。化合物13通过均苯三甲酸和4,5-二氮杂芴-9-肟氧乙酸连接三核金属簇构成了一个新颖的3,6-连接的三维网络结构。4、利用5-氧乙酸基间苯二甲酸、4,4’-联吡啶和过渡金属在水热反应条件下,合成得到六个不同结构的配位化合物: [Zn₂（OABDC）（OH）]（14） , [Cd_1.5（OABDC） （H₂O）)（2.5）]·H₂O（15） , [Cd₂Zn_OABDC)2（H₂O）)4]·3H₂O（16） , [Zn₂（OABDC）（4,4’-bpy） （OH）]·3H₂O（17） , [Cd₃（OABDC）₂（4,4’-bpy）₂（H₂O）7]·2.5H₂O （18） , [Cd₁Zn₂（OABDC）₂ （4,4’-bpy）₂（H₂O）₄]·H₂O（19）。化合物14是由三种不同类型的螺旋链构筑的三维框架结构;化合物15是由一维链柱撑（6, 3）二维平面构成的三维框架结构;化合物16是由不同的过渡金属原子和OABDC配体连接形成的二维T字形层状结构。化合物17-19是在上面的合成条件下引入了4,4’-联吡啶配体。在化合物17中,4,4’-联吡啶配体以柱撑的形式连接3,6-连接的二维层,构成了新颖的3,8-连接的三维网络结构。化合物18是通过两种非对称的螺旋链交织构成的非心对称的三维互锁超分子网络结构。对于化合物19是一个由锌镉混金属和OABDC配体构成的新颖的3,4-连接三维网络结构,其Schl·fli符号为（⁶2.8） （6.8²） （6².8³.10）。5、利用苯并三氮唑、5-氧乙酸基间苯二甲酸和过渡金属在水热条件下反应,合成了两个不同结构的配位化合物: [Zn₃（BTA）₆]（20） ,Zn₇（BTA）₇（OABDC）（μ3-OH）₂（μ₂-OH）₂·（H₂O）（21）。化合物20展示了一个从不对称四面体构筑块出发构筑手性BIK分子筛结构的金属-有机配合物:苯并三氮唑配体的空间位阻作用产生最初的手性信息,手性信息通过四条不同的手性链传递到整个骨架中。化合物21通过三齿配位的苯并三氮唑配体充当片断配体,连接金属锌构成了独特的类金属酞菁结构单元Zn₂（μ3-OH）₂·[Zn₄BTA₄],进一步通过μ2-OH基团,外围的4-连接锌原子和OABDC配体的连接构成新颖的三维框架结构。更多还原

【Abstract】 Metal-organic coordination polymers （MOCPs） as a newly-identified functional molecule-based materials, have attracted much more attentions because of their flexible tailoring, various topologies and promising applications in hydrogen storage, ion-exchange, adsorption, molecular recognization, catalysts along with optics, electrics, magnetism and enantioselective separation. According to the principle of molecular engineering, it is possible that rational design and synthesis of novel multifunctional materials by selecting certain geometric metal ions and special organic ligands. At the same time, MOCPs can be endowed with multifunctional properties by selecting functional metal ions and organic ligands with functional groups.In this dissertation, we have focused our study on the influence of the metal ions, organic ligands and secondary ligands on the building blocks and structures of MOCPs by the hydrothermal reaction. Twenty-one new coordination compounds have been synthesized by using novel organic ligands and metal ions. The study on synthetic conditions and rules for these new compounds, topological analyses, and the exploration of relationships between structures and properties for these new compounds are also carried out. These compounds have been structurally characterized by elemental analyses, IR, XRPD, TG and single crystal X-ray diffractions. In addition, the thermal stabilities, fluorescent activity and photovoltage transients of these compounds have been studied. These results will be introduced from the following five issues:1. Four novel 3D compounds, [Zn₂（BOABA）（L1）（OH）]·2H₂O（1）, [Zn₂（BOABA）（L1）（OH）]·4H₂O（2）, [Zn₃（TMA）₂（OH）]·[N（C₄H₉）₄]（3）, and [Cu₂（BTEC）（OH）]·（L1）（4）, have been synthesized using the traditional hydrothermal methods, on the basis of 4,5-didanzole-9-wo （L1） ligands, aromatic polycarboxylate ligands with different configurations, and transition metal ions. Compound 1 shows a （3, 6）-connected rutile network constructed by tetranuclear clusters and BOABA ligands. Compound 2 displays a novel （3, 6）-connected network with complex （4.6²）₂（4².6⁹.8⁴） topology, which is constructed by tetranuclear clusters and BOABA ligands. In 3, the connection between trinuclear zinc clusters （six-connected nodes） and MTA ligands （three connections） results in an infinite 3D （3, 6）-connected network with Schl·fli symbol （4.6²） （6³） (4.6¹¹.8³). Compound 4 exhibits a 4, 8-connected scu network that is made of tetranuclear clusters as eight-connected nodes and BTEC as four-connected nodes.2. Four compounds with different dimensionalities, [Cd（BDC）（L2）]（5）, [Cd₂（bpdc）₂（L2）₂]（6）, [Cd（oba）（L2）]·H₂oba（7）, and [Cd（BTEC）_0.5（L2）]·（H₂O）（8）, have been prepared under hydrothermal conditions on the basis of 4,5-didanzole-9-wo-3-methylpyridine （L2） ligands, aromatic polycarboxylate ligands with different configurations, and transition metal ions. In 5 and 6, L2 ligands link with Cd atoms to form the annular units [CdL2]2. These units are further connected through linear aromatic carboxylic acids to construct the （6, 3） sheets. Compound 5 presents a 2D-3D supramolecular network through inclined interpenetration of the （6, 3） sheets. In compound 6, two （6, 3） sheets interpenetrated into a double layer in a parallel way, and then the double layers construct an infinite 2D-3D supramolecular network through the inclined interpenetration. Compound 7 is a helical pillared 2D complex including 1D nanochannels, in which L2 and oba ligands coordinate with Cd atoms in a V-shaped mode. Compound 8 shows a novel （3, 4）-connected network with （83）.（85.10） topology constructed by Cd atoms as four-connected nods and BOABA ligands as three-connected nodes.3. Five new compounds, [Zn₂（BDC）_1.5（L3）]·H₂O（9）, [Zn₂（BDC）_0.5（m-BDC）（L3）（H₂O）]·H₂O（10）, [Zn₄（m-BDC）₄（L3）₂（OH）₂]·3H₂O（11）, [Zn₂（BTC）（L3）（H₂O）]·H₂O（12）, and [Zn₃（TMA）（L3）₂ （OH）]·2H₂O（13）, have been hydrothermally synthesized on the basis of 4,5-didanzole-9-wo-3-acetic acid ligands （L3）, aromatic polycarboxylate ligands with different configurations, and transition metal ions. Compound 9 exhibits a five-connected 3D network, which is constructed by L3 and BDC ligands linking with five-connected dinuclear zinc clusters. Compounds 10-12 possess 2D geometries constructed by L3 ligands, different aromatic polycarboxylate ligands, and zinc atoms. Compound 13 demonstrates a novel （3, 6）-connected network with （52.6） （42.55.67.7） topology, which is constructed by trinuclear zinc clusters as four-connected nods and TMA ligands as three-connected nodes.4. Six compounds, [Zn₂（OABDC）（OH）]（14）, [Cd_1.5（OABDC）（H₂O）_2.5]·H₂O（15）, [Cd₂Zn_OABDC2（H₂O）₄]·3H₂O（16）, [Zn₂（OABDC）（4,4’-bpy）（OH）]·3H₂O（17）, [Cd₃ （OABDC）₂（4,4’-bpy）₂（H₂O）7]·2.5H₂O（18）, and [CdZn₂（OABDC）₂（4,4’-bpy）₂（H₂O）4]·H₂O（19）, have been hydrothermally synthesized on the basis of 5-oxyacetateisophthalic acid （H3OABDC） ligands, 4,4’-bipyridine ligands and different transition metal ions: Compound 14 displays a new 3D framework constructed by three types of helical chains. Compound 15 also prestents a 3D framework, which is constructed from （6, 3） sheets pillared by 1D chains. Compound 16 exhibits a T-shape 2D layer resulted from OABDC ligands linking with Cd atoms. Compounds 17-19 show complex frameworks due to the introduction of bridged 4,4’-bpy ligands. Compound 17 exhibits a novel （3, 8）-connected 3D network, which is constructed from the （3, 6）-connected 2D layers pillared by 4,4’-bpy ligands. Compound 18 shows a noncentrosymmetric interlocked 3D supramolecular network based on intertwining of two kinds of asymmetric helix. Compound 19 displays a novel 3, 4-connected network with （6².8） （6.8²） （6².8³.10） topology based on OABDC ligands and mixed metals （Zn and Cd）.5. Two novel compounds, [Zn₃（BTA）₆]（20） and Zn₇（BTA）7（OABDC） （μ₃-OH）₂（μ₂-OH）₂·（H₂O）（21）, have been synthesized under hydrothermal conditions, on the basis of benzotriazole （BTA）, H3OABDC ligands and transition metal ions. Compound 20 as a novel chiral coordination polymer with a bikitaite zeolite framework has been constructed from asymmetric tetrahedral building blocks, in which the original chiralities derive from the configurational effect of benzotriazole ligands and transfer to the network through four distinct helical chains. In compound 21, an unprecedented metallophthalocyanine-like subunit, Zn₂（μ₃-OH）₂·[Zn₄BTA₄], which is constructed fromη3-BTA ligands as fragment ligands, and further linked viaμ₂-OH, outer four-connected Zn atoms, and 5-oxyacetateisophthalic acid, to form a novel three-dimensional framework.更多还原