【作者】 孙锦玉；

【导师】 赵东元；

【作者基本信息】 复旦大学 ， 物理化学， 2004， 博士

【摘要】 分子基无机网络结构材料已显示其良好的孔特性、磁性以及光、电等功能，预示着其在分离、手性拆分、催化（特别是酶催化）、光电磁分子器件等方面具有潜在的应用价值。目前，以羧酸配体构筑大孔径配位聚合物的微孔材料已成为最有吸引力的研究课题之一。大多数研究者从新的配体出发进行设计，旨在合成大孔径的配位聚合物材料，但由于新的配体的限制相应的拓扑结构缺乏变化。 本文从简单的常见的羧酸配体出发，旨在合成新拓扑结构的配位聚合物，探索其合成规律。我们通过选择一些特殊配位性质（构型或配位方式）的金属离子、调变溶剂组份和引入单官能团配体等手段，制备了37种结构不同的羧酸基配位聚合物（Metal-Carboxylate Frameworks，表示为MCF-n）。结果如下： 利用In³⁺、Sn⁴⁺等金属离子可以形成特殊配位构型如In（CO₂）₄^-、Sn（CO₂）_<sup>2-的特性，合成了四种具有新型结构的羧酸基配位聚合物：其一是H[In（p-BDC）₂]·1.5-DMF·4H₂O（MCF-1），具有开放式手性骨架的β-石英拓扑结构，其孔径为7.8；其二是金刚石拓扑的H[In（BPC）₂]·4H₂O（MCF-2），它的结构具有新型四重互穿方式；其三MCF-3的结构（H[In（m-BDC）₂]·1.0 DMF·2H₂O）属于（4，4）-网络拓扑，但具有新型的构象：在MCF-4（[Sn（SO₄）（BDC）（H₂O）]·0.8DMF）结构中，锡离子的特殊配位构型使其两维结构具有少见的二维孔道特征。结构分析结果表明，中心离子的特殊几何构型是影响羧酸基配位聚合物拓扑的关键因素之一。 根据羧酸可以与稀土离子以多种方式配位的特点，我们选择了钕、铈、镱等稀土离子与对苯二甲酸、间苯二甲酸反应，合成了四种具有新型结构的羧酸基配位聚合物：[Nd₂（p-BDC）₃（DMF）₃]·2H₂O（MCF-5），[Nd₂（m-BDC）₃（DMF）₂]·2DMF（MCF-6），[Ce₂（p-BDC）₃（DMSO）₂]·2NO₃（MCF-7），[Yb₂（m-BDC）₃（DMF）（H₂O）]·3-DMF（MCF-8）。其中MCF-7具有新型双核结点的、类ReO₃拓扑的开放式结构；而MCF-5、MCF-6、MCF-8都含有一个稀土金属共边的多面体链状单元。由于配位聚合物中羧基配位方式不同，三者结构明显不同。只有以一种羧基方式配位的MCF-5呈致密结构；羧基以两种方式配位的MCF-6具有孔径为10的一维六角孔道结构；而以四种配位方式的MCF-8却产生了一种新型的三螺旋结构。由此可见，稀土配位聚合物的结构取决于稀土离子与羧酸的配位方式。 在过渡金属与羧酸的合成体系中，我们考察了溶剂与羧酸基配位聚合物结构之间的关系。其中Zn²⁺与异烟酸，在DMF或DMSO中可以得到具有α-石英拓扑的MCF-9（[Zn（ISN）₂]·2H₂O），在乙醇中可以产生具有金刚石拓扑的MCF-10（[Zn（ISN）₂]），而在水中则得到单体配合物CP-1（[Zn（ISN）₂（H2O）₄]）。与此类似，复旦大学博士学位论文摘要隔离子与异烟酸反应，在乙醇中得到了金刚石拓扑的McF一n（[Cd-（ISN）2]·DMF·HZo），而在水中形成了单体配合物Cp一2（[Cd（ISN）2（HZO）4]）。锌离子与对苯二甲酸反应，在DMSO一EtOH（1/2）混合溶剂中，可以产生ReO3型拓扑结构的MCF一13（[Z山伽3一OH）2（t-DMSo）4勿一Bne)3]);在DMso一HZo（2/3）中得到了一种锌梭酸簇链状结构的配位聚合物[Zn切一BDC)（HZo）z].ZH20（McF一18），在水中却得到了一种单核结构单元的链状结构MCF一17（[Zn勿一BDC）（Py）（HZo）])。研究结果表明，溶剂是影响配位聚合物结构重要因素之一。 借鉴柱撑粘土的合成思想，我们成功地开发了两步法合成配位聚合物的新路线。采用层状结构的配位聚合物Zn3勿一BDC)3（HZO）2]·DMF（MCF一25）为前驱体，与对苯二甲酸配体进行二次水热合成，得到了两种新型层柱结构的配位聚合物Zn3勿一BDC)4]·Zpip（MCF一28，Pip为呱嗦）和Zn3勿一BDC)4]·4DMF·ZHZO（MCF一29）。 与沸石分子筛合成中加入F的思想类似，我们采用了单官能团配体，如HCOOH等，成功地合成了八种新型结构的竣酸基配位聚合物:[Co3（m一BDC）41·HCOOH·HZO（MCF一30）、[CoZ（HCOZ）4（HZO）4]（MCF一31）、[CoZ（m-BDC）2（DMF）3]·DMF（MCF一32）、[Fe6（BTC）2（HCOO）6（DMF）6]（MCF一33）、【Mn6（BTC）2（HCOO）6（DMF）6]（MCF一34）、[Mn6（BTC）2（HCOO）6（DMF）3]·6姚O （MCF一35）、[M伽（m一BDC）4（EtOH）（DMF）5]·ZDMF·HZO（MCF一36）、【M功（m一BDC）2-（EtoH）2（DMF）21·EtOH·践O（MCF一37）。从结构分析结果表明，单官能团配体HCOOH在合成中具有三种功能，其一，与F一离子类似，在结构中起到端基化作用;其二，与F一离子的矿化功能相似，只调节酸度、促进晶化的矿化剂作用;其三，HCOOH可以起到桥联功能，由此产生的MCF一31新型配位聚合物，其具有六联接的新型拓扑结构，其中含有一个八元环，十个六元环、四个四元环。而DMF、乙醇等其他单官能团配体只起到端基化作用。 论文的另一部分对孔道型介观网络结构和纳米沸石的微米网状有序排列作了探索性研究。通过加入辅助试剂和改变硅源的方法，利用超分子自组装原理，合成了各种形貌介观有序的孔道结构SBA一15。利用软印刷技术和溶剂辅助自组装技术、实现纳米沸石的微米网状有序排列。更多还原

【Abstract】 Coordination polymer is one of the most attractive topics of current researches. Therefore, a large number of coordination polymers with various topologies, such as diamond and ReO3, have been prepared in recent years. Apart from their aesthetically attractive structures, their inherent architectures also offer the substances the potential applications in molecular adsorption, optical or electronic molecular devices and molecular magnets. In fact, the effort for construction of coordination polymers by design of new carboxylic ligands has been essentially forced by the desire for large-pore materials, however, structural diversities of carboxylate-based coordination polymers are limited. In this dissertation, we use staple benzenecarboxylic acids such as terephthalate, metaphthalate, isonicotinate etc. as the ligands to construct brand new coordination polymers with various framework structures. Our strategies are to choose metal ions with particular geometries, regulate the composition of media and introduce the mono-functional ligands into the reaction systems:In view of the particular coordination geometries of the complex In(CO2)4" and Sn(CO2)22-, the In(III) and Sn(IV) were used as central metal ions to react with terephthalate, metaphthalate and 4,4’-biphenyldicarboxylate in DMF, producing following coordination polymers: (i) H[In(p-BDC)2]1.5DMF-4H2O (MCF-1) with quartz topology, which pore size is calculated to be 7.8 A; (ii) H[In(BPC)2]4H2O, (MCF-2) with four-fold interpenetrated diamond-like networks , (iii) H[In(m-BDC)2]-1.0DMF 2H2O (MCF-3); (iv) MCF-4 ([Sn(p-BDC)(SO4) (H2O)]-0.8DMF). The fashion of inter-penetration in MCF-2 is different from the 1/n or 4, 4 mode reported previously. MCF-3 and MCF-4 show unusual 2-dimensional structures. These results have evidenced that the frameworks of the coordination polymers are related to the particular geometry of metal ions.Four novel frameworks of coordination polymers have been also prepared by reacting rare earth metal ions such as Nd3+, Ce4+ ,Yb3+ with poly-carboxylate ligand: (i) [Nd2(P-BDC)3(DMF)3]-2H20 (MCF-5); (ii) [Nd2(m-BDC)3(DMF)2]-2DMF (MCF-6); (iii) [Ce2(p-BDC)3(DMSO)2]-2NO3 (MCF-7); (iv) [Yb2(m-BDC)3(DMF) (H2O)]-3DMF(MCF-8), of which, MCF-7 shows Re03-like topological structure with binuclear Ce-ions as the framework nodes while MCF-5, MCF-6 and MCF-8 share same chain-unit that is made up of co-edge polyhedra of rare-earth ions. However, the different coordinated models of carboxylate to rare earth ion resulted in the MCF-5 of a dense phase coordination polymer, the MCF-6 of open framework with 10 A hexagonal channels, and the MCF-8 with three-fold helical structure. Therefore, it seems that the structures of carboxylate-based coordination polymers are much dependant on the diversities of coordinate fashions of carboxylate to metal ions.We also investigated the effect of solvents on the structures of carboxylate coordination polymers of transition metals. Fourteen coodination polymers have been successfully prepared. They exhibite structural varieties produced in different solvent systems, for example, MCF-9, (Zn(ISN)2-2H2O) with the a-quartz-like open framework is formed in DMSO(DMF), MCF-10, (Zn(ISN)2) with diamondoid framework can be formed in ethanol and CP-1, (Zn(ISN)2(H2O)4) of monomer is obtained in water by the reaction of isonicotinate with Zn2+ ion, MCF-13, (Zn4(u3-OH)2(r-DMSO)4(p-BDC)3) with ReO3-like framework is built up from bicubane tetranuclear zinc blocks in mixture DMSO-ethanol (1/2), MCF-18, ([Zn(p-BDC)(H2O)2]-2H2O) with double-chain units can be obtained in DMSO-H2O (2/3) system, and MCF-17, ([Zn(p-BDC)(Py)(H2O)]) with single-chain unit is formed in water, and so on. All of these results have shown that the structural varieties are mainly dependant on the nature of the solvents used.Imitating the pillared clay, we firstly explored the synthetic strategy of two-step method for preparing novel coordination polymers, for example, a layered coordination polymer Zn3(p-BDC)3(H2O)2]-4DMF (MCF-25) was used as a precursor to re更多还原