5-[4-(4-吡啶基)苯乙烯基]-1,3-苯二甲酸铜配合物的结构及性质研究

Structure and properties of metal-organic frameworks with 5-[4-(pyridin-4-yl)styryl]-1,3-benzenedicarboxylate ligand

设计合成了一种新型有机配体5-[4-(4-吡啶基)苯乙烯基]-1,3-苯二甲酸(H2L),并将其与Cu(NO3)2·3H2O在不同条件下反应合成了两种不同结构的配位聚合物{[CuL]·H2O}n(1)和{[Cu2L2]·H2O}n(2).配合物1为utp型有孔道的金属有机框架化合物(MOF)结构,配合物2为含双核铜单元的rtl型拓扑结构.研究发现,1对N2和CO2均未表现出吸附性质,而与其拓扑结构相同的配合物{[Cu(INAIP)]·2H2O}n(H2INAIP=5-异烟酰胺基异酞酸)却有很好的CO2吸附性能.为理解它们的构效关系,从实验和理论计算两方面对这两种化合物进行了比较研究,证实此差异源于配体中连接羧酸和吡啶基的共轭官能团,其中1的共轭官能团为苯乙烯基,而{[Cu(INAIP)]·2H2O}n中的官能团为酰胺基.实验和理论计算的结果表明,酰胺基对CO2吸附起了重要作用.另外,对配合物2的磁性质进行了研究,结果表明,该化合物具有反铁磁性相互作用.

A new organic ligand 5-[4-（pyridin-4-yl）styryl]-l,3-benzenedicarboxylic acid （H2L） was prepared and its metal-organic coordination polymers { [CuL]＇H20}, （1） and {[Cu2L2]＇H20}n （2） were prepared by reactions of H2L with Cu（NO3）2＂3H20 under different conditions. Complex 1 with utp-type topology possesses large solvent void, while 2 with a binuclear Cu subunit has an rtl-type topology. Complex 1 exhibited no N2 and CO2 uptake. However, its isoreticular structure { [Cu（INAIP）]＇2H20 }n [H2INAIP = 5-（isonicotinamido）isophthalic acid] showed much larger CO2 uptake. In order to get the relationship between the frameworks and sorption properties, we performed experimental and GCMC calculation investigation on both of them. The only difference between {[Cu（INAIP）] · 2H20}n and 1 was the replacement of the amide group from H2INAIP with an styryl group. Thus the amide group plays very important role in the CO2 sorption property of { [Cu（INAIP）]·2H20}n. Furthermore, the magnetic property of complex 2 was also investigated, and results indicated that it was with antiferromagnetic interactions.