以5-甲基-3-吡唑甲酸为配体构建的具有六方孔道的钴(Ⅱ)、镍(Ⅱ)超分子化合物:合成、晶体结构和性质

摘要

The new monomeric complexes of [M(MPA)2(H2O)2] (1:M=Co; 2:M=Ni) (HMPA=5-methyl-IH-pyrazole-3-carboxylic acid) were synthesized by the reaction of 5-methyl-1H-pyrazole-3-carboxylic acid with CoCl2·6H2O and Ni(NO3)2· 6H2O,respectively.The compounds were characterized by elemental analysis,IR spectra,single crystal Xray diffraction.The structural parameters of 1 and 2 were analyzed as follows:1,Hexagonal,R(3)c,a=1.48394 (4) nm,b=1.483 94 (4) nm,c=3.207 66 (6) nm,V=6.1172 (3) nm3,Z=18; 2,Hexagonal,R3c,a=1.466 53(14) nm,b=1.466 53(14) nm,c=3.243 0(6) nm,V=6.040 3(14) nm3,Z=18.Metal ions have all octahedral geometry coordinated by two nitrogen atoms and two oxygen atoms from two MPA-ligands,two oxygen atoms from two H2O molecules.In both complexes,the independent components [M (MPA)2(H2O)2] are connected by intermolecular hydrogen bonds to form a three-dimensional architecture with hexagonal channels.Thermogravimetric analyses show that 1 and 2 have higher thermal stability.In addition,the luminescent properties and electrochemical properties of complexes 1 and 2 have also been investigated.CCDC:900677,1; 900678,2.%利用5-甲基-3-吡唑甲酸,分别与CoCl2·6H2O和Ni (NO3)2·6H2O反应,得到了配合物[M(MPA)2(H2O)2] (1:M =Co;2:M =Ni)(HMPA=5-甲基-3-吡唑甲酸).用元素分析、红外光谱、X-单晶衍射结构分析对其进行了表征.配合物1和2的晶体结构参数如下:配合物1和2的晶体部属于六方品系,空间群为R(3)c.配合物1的品胞参数为a=1.483 94 (4) nm,b=1.483 94 (4) nm,c=3.207 66(6) nm,V=6.117 2(3) nm3,Z=18；配合物2的品胞参数为a=1.466 53(14) nm,b=1.466 53(14) nm,c=3.243 0(6) nm,V=6.04 03(14) nm3,Z=18.金属离子与来自2个5-甲基-3-吡唑甲酸配体中的2个氮原子及2个氧原子,2个水分子中的2个氧原子配位,形成八面体配位构型.配合物中的独立结构单元[M(MPA)2(H2O)2]通过分子间氢键形成具有六方孔道的三维结构.热重分析表明配合物1和2具有较高的热稳定性.此外,考察了配合物1和2的荧光和电化学性质.CCDC:900677,1；900678,2.