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三种新型亚硒酸铜(II)和亚碲酸铜(II)混合金属的结构与磁性研究。

Structural and magnetic studies on three new mixed metal copper(II) selenites and tellurites.

作者信息

Cao Xue-Li, Kong Fang, He Zhang-Zhen, Mao Jiang-Gao

机构信息

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China.

出版信息

Dalton Trans. 2015 Jul 7;44(25):11420-8. doi: 10.1039/c5dt01257k.

Abstract

Three new transition metal copper(II) selenites or tellurites, namely, CdCu(SeO3)2 (1), HgCu(SeO3)2 ()2, and Hg2Cu3(Te3O8)2 (3), have been obtained by conventional hydrothermal reactions of CdO (or Hg2Cl2), CuO and SeO2 (or TeO2). Compounds 1 and 2 are isostructural and crystallize in P2(1)/c. Their structures feature a 3D anionic framework of Cu(SeO3)2(2-) with 1D channels of eight-membered rings (MRs) along the c-axis and a-axis, respectively, which are filled by Cd(2+) or Hg(2+) cations. Compound 3 crystallizes in a tetragonal system of space group P42(1)2. Its structure is characterized by a Cu3(Te3O8)2 honeycomb layer composed of Te3O8 anions interconnected by Cu(2+) ions with 1D channels of 8-MRs along the c-axis. TOPOS analysis indicates that the copper(ii) tellurite layer exhibits a new topological structure with a Schläfli symbol of {4(6)·8(9)}(2){4(6)}(3). The above anionic copper(II) tellurite layers are further linked by dumbbell Hg2(2+) cations to form a novel 3D framework. Magnetic measurements based on magnetic susceptibility and heat capacity indicate that compounds 1 and 2 show a spin-singlet ground state with a spin gap based on the Cu2O8 dimeric model, whereas compound e3 xhibits a 2D spin-system with an antiferromagnetic ordering around 25 K correlated with its honeycomb Cu3(Te3O8)2 layer. Furthermore, crystalline structures, thermal stabilities, IR spectra and UV-Vis diffuse reflectance spectra have also been studied.

摘要

通过氧化镉(或氯化汞)、氧化铜与二氧化硒(或二氧化碲)的常规水热反应,已制得三种新型过渡金属亚硒酸铜(II)或亚碲酸铜(II),即CdCu(SeO3)2 (1)、HgCu(SeO3)2 (2)和Hg2Cu3(Te3O8)2 (3)。化合物1和2结构相同,都结晶于P2(1)/c空间群。它们的结构特点是具有Cu(SeO3)2(2-)的三维阴离子骨架,分别沿c轴和a轴有八元环(MRs)的一维通道,这些通道由Cd(2+)或Hg(2+)阳离子填充。化合物3结晶于空间群为P42(1)2的四方晶系。其结构特征是由Te3O8阴离子通过Cu(2+)离子相互连接而成的Cu3(Te3O8)2蜂窝层,沿c轴有8-MRs的一维通道。TOPOS分析表明,亚碲酸铜(II)层呈现出一种新的拓扑结构,施莱夫利符号为{4(6)·8(9)}(2){4(6)}(3)。上述阴离子亚碲酸铜(II)层通过哑铃状Hg2(2+)阳离子进一步连接,形成一种新型三维骨架。基于磁化率和热容量的磁性测量表明,化合物1和2基于Cu2O8二聚体模型呈现出具有自旋能隙的自旋单重基态,而化合物3表现出二维自旋系统,在约25 K时具有反铁磁有序,这与其蜂窝状Cu3(Te3O8)2层相关。此外,还研究了晶体结构、热稳定性、红外光谱和紫外可见漫反射光谱。

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