2种蓝矾衍生物的合成、结构及光谱性质

Solvothermal Synthesis,Structures and Spectroscopic Properties of Two Chalcanthite Derivatives

分别采用咪唑（im）和2,2′-联吡啶（bpy）为配体与五水硫酸铜在硝酸酸性乙醇/DMF介质中反应合成了[Cu（im）4SO4]n（1）和在硝酸酸性DMF介质中合成了[Cu（bpy）（H2O）2SO4]n（2）2种蓝矾衍生物,产率分别为67%和82%。考察了体系硝酸量对产物结构的影响。结果表明,体系中加入的硝酸量分别控制在0.35-0.6 mmol和1.2-1.45 mmol时,可得到纯相的化合物1和化合物2。通过元素分析、红外光谱、热重、电感耦合等离子体发射光谱、X射线粉末衍射及X射线单晶衍射结构分析测试技术对其进行了表征。结构分析表明,化合物1和化合物2均属单斜晶系,C2/C空间群,具有蓝矾特征结构,受各自配体的空间位阻效应影响。化合物1呈一维＂之＂字链状结构,化合物2为一维＂一＂字链结构。二者的粉末UV-Vis漫反射光谱分析表明,2个化合物在可见区吸收峰归属于Cu（Ⅱ）离子的d-d跃迁;近紫外区,化合物1的吸收峰归属于配体（im）→Cu（Ⅱ）的电荷转移,化合物2的吸收峰归属于bpy的π→π＊跃迁。

Two compounds, [Cu（im）4SO4]n（1） and [ Cu （bpy） （ H2O） 2SO4 ]n （2） （ im = imidazole, bpy = 2, 2＇-bipyridine）, were synthesized in ethanol/DMF systems with HNO3 in 67% and 82% yields, respectively. The relation between the crystal structure and acidity of the reaction system were investigated. As 0. 35- 0. 6 mmol or 1.2 - 1.45 mmol HNO3 was added to the reaction system pure compound 1 or 2, respectively, was obtained. And they were further characterized by elemental analysis, IR, UV-Vis reflection spectra, inductively coupled plasma （ICP）, TGA, X-ray powder diffraction and X-ray crystallography diffraction. The crystal structure analyses revealed that they all belong to the monoclinic system with space group C2/C, possessing chalcanthite-like configuration. Compound 1 exhibits a 1 D zigzag chain structure, while 2 exhibits 1 D linear chain, which is resulted from different ligands. UV-Vis reflection spectra of the two compounds indicated that the absorption bands in visible region are from the d-d transitions of copper（ Ⅱ ） ions and the absorption bands in ultraviolet region correspond to ligand→copper（ Ⅱ ） charge transfer and π→π＊ transition for compounds 1 and 2, respectively.