Karmakar Anirban, Guedes da Silva M Fátima C, Pombeiro Armando J L
Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal.
Dalton Trans. 2014 Jun 7;43(21):7795-810. doi: 10.1039/c4dt00219a. Epub 2014 Apr 9.
Three new compounds bearing different flexible side functional groups, viz. 2-acetamidoterephthalic acid (H2L1), 2-propionamidoterephthalic acid (H2L2) and 2-benzamidoterephthalic acid (H2L3), were synthesized and their coordination reactions with zinc(II) were studied. X-ray crystallography showed the formation of novel metal organic frameworks with different dimensionalities, where the side functional groups of amidoterephthalic acid and/or auxiliary ligands were found to play significant roles. These frameworks [Zn2(L1)2(4,4'-bipyridine)2(H2O)(DMF)]n (1), [Zn4(L2)3(OH)2(DMF)2(H2O)2]n (2) and [Zn(L3)(H2O)2]n·n/2(1,4-dioxane) (3) act as heterogeneous polymeric solid catalysts not only for the diastereoselective nitroaldol (Henry) reaction of different aldehydes with nitroalkanes but also for transesterification reactions. These MOF-based heterogeneous catalysts can be recycled without losing their activity.
合成了三种带有不同柔性侧链官能团的新化合物，即2-乙酰氨基对苯二甲酸（H2L1）、2-丙酰氨基对苯二甲酸（H2L2）和2-苯甲酰氨基对苯二甲酸（H2L3），并研究了它们与锌（II）的配位反应。X射线晶体学表明形成了具有不同维度的新型金属有机框架，其中发现对苯二甲酰胺酸的侧链官能团和/或辅助配体起着重要作用。这些框架[Zn2(L1)2(4,4'-联吡啶)2(H2O)(DMF)]n (1)、[Zn4(L2)3(OH)2(DMF)2(H2O)2]n (2) 和 [Zn(L3)(H2O)2]n·n/2(1,4-二氧六环) (3) 不仅作为多相聚合物固体催化剂用于不同醛与硝基烷烃的非对映选择性硝基醇（亨利）反应，还用于酯交换反应。这些基于金属有机框架的多相催化剂可以循环使用而不丧失其活性。
