一种基于多金属氧酸盐的三核铜（II）三唑框架的合成与性质

Synthesis and properties of a POM-based trinuclear copper(ii) triazole framework.

作者信息

Xu Li, Lu Ying, Huang Liping, Li Xiaohui, Wang Shuang, Zhang Zhong, Liu Shuxia

机构信息

Key Laboratory of Polyoxometalate Science of the Ministry of Education, College of Chemistry, Northeast Normal University Changchun Jilin 130024 China

出版信息

RSC Adv. 2018 Jan 9;8(4):2034-2040. doi: 10.1039/c7ra12150d. eCollection 2018 Jan 5.

A novel POM-based trinuclear copper(ii) triazole framework, namely, [H{Cu(trz)(μ-OH)}MoO]·3HO (1) was isolated using a hydrothermal method, which displays a 3D network constructed from trinuclear copper(ii) units and triazole ligands with [MoO] anions as templates. 1 has been identified by single crystal X-ray diffraction, elemental analysis, thermogravimetric analysis, powder X-ray diffraction and FT-IR. Magnetic studies indicate that antiferromagnetic interactions exist in 1. In addition, 1 exhibits good Lewis acid catalytic activity for the synthesis of cyclohexanone ethylene ketal with 95% conversion. The HOMO-LUMO gap ( ) of 1 is 2.34 eV calculated using the Kubelka-Munk equation (), indicating that its forbidden bandwidth belongs to the semiconductor category. Visible-light photodegradation of RhB catalyzed by 1 was investigated, which shows high activity with an above 98% degradation rate.

采用水热法分离得到一种新型的基于多金属氧酸盐的三核铜（II）三唑骨架，即[H{Cu(trz)(μ-OH)}MoO]·3HO（1），它呈现出由三核铜（II）单元和三唑配体构建的三维网络，以[MoO]阴离子为模板。通过单晶X射线衍射、元素分析、热重分析、粉末X射线衍射和傅里叶变换红外光谱对1进行了表征。磁性研究表明1中存在反铁磁相互作用。此外，1对环己酮缩乙二酮的合成表现出良好的路易斯酸催化活性，转化率为95%。利用库贝尔卡-蒙克方程（）计算得出1的HOMO-LUMO能隙（）为2.34 eV，表明其禁带宽度属于半导体范畴。研究了1催化的罗丹明B的可见光光降解，其降解率高于98%，显示出高活性。