三维网状有机-无机杂化型DABCO锰配合物的合成及性能研究

Synthesis and properties of three-dimensional network organic-inorganic hybrid DABCO manganese complex

室温下以1,4-二氮杂二环[2.2.2]辛烷-甲基氯化物[DABCO-CH_(2)Cl]^(+)·Cl^(-)、MnCl_(2)·4H_(2)O和氢溴酸为原料,在甲醇和水的混合溶液中以缓慢蒸发方式,得到一种氢键三维网状结构有机-无机杂化型锰配合物[HDABCO-CH_(2)Cl]·MnBr_(4)(1),通过单晶X射线衍射仪、傅里叶变换红外光谱仪、粉末X射线衍射仪、热重分析仪、介电性能测试仪对晶体材料的结构、热性能和电性能进行分析和测试。单晶结构分析表明:合成的化合物属于单斜晶系,空间群为P21/n,其中[HDABCO-CH_(2)Cl]^(2+)阳离子和[MnBr_(4)]^(2-)四面体阴离子在晶体内部通过氢键相互作用形成三维网状结构;随着温度的改变,[HDABCO-CH_(2)Cl]^(2+)阳离子发生扭动、[MnBr_(4)]2-四面体阴离子发生伸缩变形,引起晶体在240~270K范围内产生显著的可逆介电异常现象。

A hydrogen-bonded three-dimensional network organic-inorganic hybrid manganese complex[HDABCO-CH_(2)Cl]·MnBr_(4)(1)was obtained with[DABCO-CH_(2)Cl]^(+)·Cl^(-),MnCl_(2)·4H_(2)O and hydrobromic acid as raw materials in a mixed solution of methanol and water by slow evaporation method at room temperature.The structure,thermal and electrical properties of the crystalline material were analyzed and tested by single crystal X-ray diffraction,the Fourier transform infrared spectroscopy(FT-IR),powder X-ray diffraction,thermogravimetric analysis(TG),and variable temperature-frequency dielectric constant test.The single crystal structure analysis showed that the synthesized compound belonged to monoclinic crystal system with space group P21/n,in which[HDABCO-CH_(2)Cl]^(2+)cations and[MnBr_(4)]^(2-)tetrahedral anions formed a three-dimensional network structure through hydrogen bonding interactions inside the crystal.With the change of temperature,the[HDABCO-CH_(2)Cl]^(2+)cation twisted and the[MnBr_(4)]^(2-) tetrahedral anion produced a stretching deformation,causing a significant reversible dielectric anomaly in the crystal in the temperature range of 240~270K.