摘    要金属有机骨架是近十多年发展起来的材料, 是由无机金属离子（或金属离子簇）和有机配体连接形成的一种多孔晶体材料。金属有机骨架种类繁多,构成金属有机框架物的配体可以是有机酸, 也可以是有机碱, 还可以是其他特殊的官能团。本论文设计合成了含L-吡咯烷手性功能基团的多羧酸刚性有机配体H2L，该配体与过渡金属离子反应得到了金属有机骨架多孔配合物[Zr6O4(OH)4(L)6] ，采用红外、H-NMR、XRD和热重等对有机配体和配合物进行表征。配合物骨架中含有L-吡咯烷催化位点，因而，开展了配合物对环己酮和对硝基苯甲醛不对称Aldol反应的催化性能研究。实验结果表明配合物催化的Aldol反应产率为53-63%。与以往L-吡咯烷衍生物小分子催化剂或者含L-吡咯烷的MOFs催化效果不同，设计的配合物催化的产物构型均以顺式为主。对配合物进行重复利用，作为非均相催化剂，它克服了小分子催化剂难以回收利用的缺点，且表现出高效的顺势选择性催化效果(dr=99:1)。90089

毕业论文关键词：手性；金属有机骨架；不对称催化；

Abstract Metal organic frameworks (MOFs) as a new type of organic/inorganic hybrid materials have attracted great focus of scientists in almost twenty years。 It is composed of organic ligands and inorganic metal units and generally has a varied to pological structure and unique physical/chemical properties。 It can choose different ligands and metal ions, or change the strategy of synthesis to adjust the size, shape and structure of porous structure。 In this paper, four polycarboxylic acid rigid organic ligands (H3L) containing L-pyrrolidine chiral groups were designed and synthesized,and then let them react with metal ions to synthesize  chiral porous metal organic frameworks: [Zr6O4(OH)4(L)6]。 The organic ligands and complexes were characterized by IR, NMR, XRD and thermogravimetry。 The catalytic properties of complexes on the asymmetric Aldol reaction of cyclohexanone and p-nitrobenzaldehyde were carried out in the ligands stable skeletons containing L-pyrrolidine catalytic sites。 The experimental results show that the yield of Aldol reaction catalyzed by complexes is 53-63%。 In contrast to the catalytic effect of L-pyrrolidine derivatives in the past, or the catalytic effect of MOFs containing L-pyrrolidine, several of the complexes of our products were dominated by cis。 The complex is used as a heterogeneous catalyst, which overcomes the shortcomings of the small molecule catalyst which is difficult to be recycled and exhibits an efficient homeopathic selective catalytic effect (dr = 99: 1)。

Keywords：chirality; metal-organic frameworks; asymmetric catalysis

目录

 1。 绪论 6

1。1引言 6

1。2金属有机骨架的分类 6

1。3金属有机骨架化合物的合成 6

1。3。1金属离子的选择 6

1。3。2有机配体的选择 7

1。3。3配合物的合成方法 8

1。4金属有机骨架化合物应用 9

1。4。1气体吸附 9

1。4。2光学材料 9

1。4。3不对称催化 9

2。  含L-吡咯烷羧酸配体金属有机骨架的设计合成及催化不对称Aldol反应的研究 12

2。1 引言 12

2。2 实验部分