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(英文)

Cobalt and Nickel Supramolecular Complexes with Hexagonal Channels Constructed from 5-Methyl-1H-Pyrazole-3-Carboxylic Acid: Synthesis, Crystal Structures and Properties

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的晶体都属于六方晶系,空间群为R3c。配合物1的晶胞参数为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的晶胞参数为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。

The new monomeric complexes of [M（MPA）2（H2O）2] （1： M=Co; 2： M=Ni） （HMPA=5-methyl-lH-pyrazole-3- carboxylic acid） were synthesized by the reaction of 5-methyl-1H-pyrazole-3-carboxylic acid with COC12·6H2O and Ni（NO3）：2·6H2O, respectively. The compounds were characterized by elemental analysis, IR spectra, single crystal X- ray diffraction. The structural parameters of 1 and 2 were analyzed as follows： 1, Hexagonal, R3c, 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 H20 molecules. In both complexes, the independent components [M（MPA）2（H20）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 have also been investigated. CCDC： 900677, 1; 900678, 2. and electrochemical properties of complexes 1 and 2