【作者】 王华；

【导师】 韩金玉；

【作者基本信息】 天津大学 ， 化学工艺， 2007， 博士

【摘要】 金属-有机配位聚合物作为新一代多孔材料,兼具高比表面积、孔道易调控、骨架结构多样、易于功能化等特性,得到了学术界和工业界的广泛重视。本文对柔性、刚性有机羧酸配体的新型金属-有机配位聚合物的合成、表征及催化性能进行了研究。选择亚氨基二乙酸、丁二酸、己二酸等碳链长度适中的柔性链二羧酸为配体,通过合理引入含氮杂环配体,合成了9种新型配位聚合物:[Mn（iminodiacetate）]_n（1）、[Cu（succinate）（imidazole）₂]_n（2）、[Cd（succinate）（4,4’–bipy）]_n（3）、[Co（adipate）（4,4′-bipy）]_n（4）、{[Cd₄（adipate）₄（1,10’-phen）₄]·12H₂O}n （5）、{[Y₂（succinate）₃·（H₂O）₂]·0.5 H₂O}n （6）、[Nd₂（succinate）₃（H₂O）₂]n（7）、{[Nd（succinat -e）1.5·（H2O）]·1.25H₂O}n（8）、[La₂（succinate）₃ （H₂O）₂]n （10）。配合物（1）的热稳定性好,450℃以上发生骨架分解;配合物（5）中具有新颖的螺旋链结构,其中Cd2+采取了六、七两种配位数。单晶衍射晶体结构分析表明,柔性链二羧酸配体易于连接金属中心形成双核或多核单元,提高了配合物的稳定性;当金属中心为配位数高的稀土金属离子时,柔性链二羧酸配体采取五齿或六齿两种配位模式,碳链空间取向多变,形成了同分异构的配位聚合物（7）和（8）,而且复杂的碳链取向在一定程度上阻碍了第二配体参与配位。选择间苯二甲酸、均苯三甲酸等刚性芳香羧酸配体,通过合理引入竞争性配体,合成5种新型配位聚合物:{[Nd₂（BDC）₃（1,10’-phen）（H₂O）]·0.5H₂O}n （9）、{[Co₃（BTC）₂（H₂O）₁₂]·0.25H₂O}n（11）、[Ni₂Zn（BTC）₂（H₂O）₁₂]n（12）、[Zn（BTC）（2,2’-bipy）H₂O]n（13）、{[Zn₂（HBDC）₂（BDC）]·（1,10’-phen）·1.5H₂O}n（14）。配合物（12）是新颖的异核金属中心配位聚合物。单晶衍射晶体分析结果表明,两种刚性羧酸配体的羧基数目不同,在连接金属中心时呈现出各自的特点;螯合配体的引入,会降低金属中心的配位数;形成的配合物中具有复杂的氢键网络,通过氢键作用构筑三维网络结构;同时荧光分析表明芳香羧酸配体对稀土离子的发光效率和荧光光谱特征峰位都有影响。缩醛反应研究表明四种配合物[（6）, （8）, （11）,（12）]都具有较好的酸催化活性,且选择性高,其中使用[Ni2Zn（BTC）2]n（12）时苯甲醛转化率达81.3%;配合物（2）[Cu（succinate）（imidazole）2]n在常温下即可催化苯甲醇的氧化反应,其催化活性随着反应温度提高而增强,但选择性氧化性能降低。更多还原

【Abstract】 Metal-Organic frameworks, as a new category of porous materials, have the properties of high specific surface area, highly designable channel, versatile structures and easily functionalized frameworks. All this leads to the widespread attention both in academia and industry. In this paper, the synthesis, characterization and the catalytic performance of the coordinated polymers constructed by the flexible or rigid carboxylic ligands were studied.Nine kinds of coordination polymers are constructed from the assembly reaction of the metal ion and the flexible dicarboxylic acid(iminodiacetic acid, succinic acid and adipic acid) in the presence of additional nitric heterocyclic ligands. [Mn(iminodiacetate)]n(1), [Cu(succinate)(imidazole)2]n(2), [Cd(succinate)(4,4’-bipy)]n(3), [Co(adipate)(4,4′-bipy)]n(4), {[Cd4(adipate)4(1,10’-phen)4]·12H2O}n(5), {[Y2(succinate)3·(H2O)2]·0.5H2O}n(6), [Nd2(succinate)3(H2O)2]n(7), {[Nd(succinat -e)1.5·(H2O)]·1.25H2O}n(8), [La2(succinate)3(H2O)2]n(10). The coordination polymer(1) shows good thermal stability for its high decomposition temperature at 450℃. The coordination polymer (5) has a double-strand helical chain structure, and Cd2+ adopted six and seven coordinated numbers.The crystal structure analysis showed that the flexible dicarboxylate ligands tend to connect the metal ions to form bi- or poly-nuclear structure unit, which could be a beneficial for high thermal stability. When the high coordinated rare-earth metal ions were employed, the flexible dicarboxylate ligands adopted five- or six-dentate coordinated fashion. The diverse extending direction of the flexible chain could give rise to form isomerous complex (coordination polymer (7) and coordination polymer (8)), and it also prevent the additional ligand from coordination to some extent.Five kinds of coordination polymers are synthsized from the assembly reaction of the metal ion and the rigid aromatic carboxylic acid (1,3,5-benzenetricarboxylic acid (H3BTC) and 1,3-benzenedicarboxylic acid (H2BDC)) in the presence of additional competition ligands. {[Nd2(BDC)3(1,10’-phen)(H2O)]·0.5H2O}n(9), [Co3(BTC)2 (H2O)12]·0.25H2O}n(11), [Ni2Zn(BTC)2(H2O)12]n(12), [Zn(BTC)(2,2’-bipy)H2O]n (13),{[Zn2(HBDC)2(BDC)]·(1,10’-phen)·1.5H2O}n (14). The coordination polymer (12) is a novel heterometallic complex.The crystal structure analysis indicated that two aromatic carboxylate ligands but have different coordination character for their different carboxyl numbers; The chelate bipy-like ligands could reduce coordination numbers of metal ions; All these five coordination polymers have various hydrogen bonds networks, by which 3D framework are constructed; The luminescence spectra indicated the aromatic carboxylate ligand could influence the luminescence intensity and the peak positions.In the aspect of catalytic perfomance of MOFs: four coordination polymers [(6), (8), (11) and (12)]are used as catalysts in the accetalization of benzaldehyde with trimethylorthoformate, all of them showed good catalytic activity and high selectivity. The conversion of benzaldehyde reached 81.3% when catalyzed by [Ni2Zn(BTC)2]n(12). The coordination polymer (2) [Cu(succinate)(imidazole)2]n could catalyze the oxidation of benzyl alcohol at room temperature. The catalytic activity was improved with the increasing temperature, while the selectivity of benzaldehyde decreased.更多还原