三个基于Wells-Dawson型多酸的三核铜簇的合成、结构及性能
Syntheses, Structures and Properties of Three Tri-nuclear Copper Clusters Based on Wells-Dawson Polyoxometalate
作者单位E-mail
应俊 渤海大学化学系, 锦州 121013 ying@bhu.edu.cn 
宁亚莉 渤海大学化学系, 锦州 121013  
侯雪 渤海大学化学系, 锦州 121013  
田爱香 渤海大学化学系, 锦州 121013  
摘要: 在水热条件下,通过Wells-Dawson型多酸[As2W18O62]6-、氯化铜(CuCl2·2H2O)和5-(4-吡啶基)-1H-四氮唑(4-ptz)的反应,在同一反应釜中合成出2个结构完全不同的、都包含三核铜簇的多酸基化合物[Cu3(4-ptz)4(H2O)7(As2W18O62)]·42H2O(1)和[Cu3(4-ptz)5(H2O)5(As2W18O62)]·47H2O(2);当我们以另一种Wells-Dawson型多酸[P2W18O62]6-、氯化铜(CuCl2·2H2O)和5-(3-吡啶基)-1H-四氮唑(3-ptz)反应,获得了另一种多酸基三核铜簇化合物[Cu3(3-ptz)4(H2O)8(P2W18O62)]·33H2O(3)。X射线单晶衍射结果表明,化合物1为多酸单支撑三核铜簇的悬臂式结构,化合物2的多阴离子被三核铜簇交替连接形成一维链式结构,而化合物3为多阴离子和三核铜簇形成的孤立结构。吡啶-四氮唑类配体(3-ptz和4-ptz)是形成化合物1~3中三核铜簇的重要结构因素。同时,研究了3个化合物的电化学以及光催化性能。
关键词: Wells-Dawson型多酸  多核铜簇  水热合成  电化学  光催化
基金项目: 国家自然科学基金(No.21571023)和辽宁省高等学校青年学者成长计划(No.LJQ2012097)资助项目。
Abstract: Through using Wells-Dawson type anion [As2W18O62]6-, CuCl2·2H2O and 5-(4-pyridyl)-1H-tetrazole (4-ptz), two different POM-based compounds containing tri-nuclear copper clusters were synthesized in one-pot under hydrothermal conditions, namely [Cu3(4-ptz)4(H2O)7(As2W18O62)]·42H2O (1) and [Cu3(4-ptz)5(H2O)5(As2W18O62)]·47H2O (2). When we used another Wells-Dawson anion [P2W18O62]6-, CuCl2·2H2O and 5-(3-pyridyl)-1H-tetrazole (3-ptz), another POM-based tri-nuclear copper cluster was also obtained, namely [Cu3(3-ptz)4(H2O)8(P2W18O62)]·33H2O (3). Single crystal X-ray diffraction shows that compound 1 is a tri-nuclear copper cluster supporting pendent structure, and compound 2 is a one dimensional chain with anions and tri-nuclear copper clusters arranging alternately, while compound 3 is a discrete structure containing anions and tri-nuclear copper clusters. 3-ptz and 4-ptz are important structural factors for constructing tri-nuclear copper clusters in compounds 1~3. The electrochemical and photocatalytic activities of the title compounds have been studied. CCDC: 1416806, 1; 1406807, 2; 1406808, 3.
Keywords: Wells-Dawson polyoxometalate  multi-nuclear copper cluster  hydrothermal synthesis  electrochemistry  photocatalysis
投稿时间:2015-09-15 修订日期:2015-11-28
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应俊,宁亚莉,侯雪,田爱香.三个基于Wells-Dawson型多酸的三核铜簇的合成、结构及性能[J].无机化学学报,2016,32(2):267-274.
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