铬酸根桥联Cu(Ⅱ)/Ni(Ⅱ)链状配位聚合物的合成及性质  

Synthesis and Characterization of Chromate Cu(Ⅱ)/Ni(Ⅱ) Chain Complexes

作　　者：蔡良圆[1] 齐琪[2] 杨春[3] 江山[1] 姜谦[1] 王庆伦[1] 任红霞[2] 

机构地区：[1]南开大学化学系,天津300071 [2]南开大学先进能源材料化学教育部重点实验室,天津300071 [3]河北工业大学化工学院,天津300130

出　　处：《高等学校化学学报》2013年第3期520-526,共7页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21071085;21101096;90922032);天津市自然科学基金(批准号:11JCYBJC03500);河北省自然科学基金(批准号:B2012202106)资助

摘　　要：设计合成了2个一维链状铬酸根桥连的配位聚合物(NH4)2[Cu(NH3)2(CrO4)2](1)和(NH4)2.[Ni(NH3)2(CrO4)2](2),并对其进行了X射线单晶结构分析、热重-差热分析和多种磁学测试.晶体结构分析表明,2个配合物的晶体均属于三斜晶系,空间群均为P1.配合物1的晶胞参数为:a=0.59090(12)nm,b=0.6929(3)nm,c=0.73740(15)nm,α=107.03(4)°,β=92.79(3)°,γ=112.44(2)°;配合物2的晶胞参数为:a=0.56987(7)nm,b=0.69972(9)nm,c=0.73335(8)nm,α=104.929(3)°,β=96.121(3)°,γ=112.325(4)°.热重分析结果表明,配合物1和2均在150℃左右开始分解,生成H2Cr2CuO5和H2Cr2NiO5,在410℃以上继续分解,脱水得到相应的氧化物.配合物的变温磁化率测试结果表明,相邻Cu(Ⅱ)离子(配合物1)或Ni(Ⅱ)离子(配合物2)之间存在较弱的反铁磁相互作用;低温变场和交流磁化率测试结果表明,2个配合物均为反铁磁体.Two new one-dimensional chain complexes,（NH4）2[Cu（NH3）2（CrO4）2]（1） and（NH4）2·[Ni（NH3）2（CrO4）2]（2）,were obtained by mixing copper nitrate or nickel nitrate with the same molar of ammonium dichromate in ammonia water at room temperature,and they were characterized by single-crystal X-ray diffraction（XRD）,thermogravimetric analysis（TGA） and differential thermal analysis（DTA）.Furthermore,the complexes were magnetically characterized by temperature-dependent magnetic susceptibility,field-dependent magnetization,and alternate current（AC） magnetic measurements.The structure analysis results show that crystals of both complexes are triclinic,space group P1 with a=0.59090（12） nm,b=0.6929（3） nm,c=0.73740（15） nm,α=107.03（4）°,β=92.79（3）°,γ=112.44（2）° for Cu（Ⅱ） complex and a=0.56987（7） nm,b=0.69972（9） nm,c=0.73335（8） nm,α=104.929（3）°,β=96.7121（3）°,γ=112.325（4）° for Ni（Ⅱ） complex.In the crystal structure,the [M（NH3）2]2＋ units are linked by two chromato bridges,forming an eight-member ring.As a whole,both complexes have one-dimensional chain structures.The two complexes began to break down as the temperature gradually reached 150 ℃ or so,leaving behind H2Cr2CuO5 and H2Cr2NiO5,and afterwards they are dehydrated at above 410 ℃.The temperature-dependent magnetic susceptibilities were measured in the range of 2—300 K,which implies a weak antiferromagnetic interaction between the adjacent mental ions.The field-dependent magnetization and AC magnetic measurements indicate that the two complexes are both antiferromagnets.

关 键 词：一维结构 配位聚合物 晶体结构 热分析 磁性表征 

分 类 号：O614[理学—无机化学]