三个基于Wells-Dawson型多酸的三核铜簇的合成、结构及性能

在水热条件下,通过Wells-Dawson型多酸As_2W_(18)O_(62)]6-、氯化铜(CuCl_2·2H_2O)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(H_2O)7(As_2W_(18)O_(62))]·42H_2O(1)和Cu3(4-ptz)5(H_2O)5(As_2W_(18)O_(62))]·47H_2O(2);当我们以另一种Wells-Dawson型多酸P_2W_(18)O_(62)]6-、氯化铜(CuCl_2·2H_2O)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(H_2O)8(P_2W_(18)O_(62))]·33H_2O(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。

Syntheses, Structures and Properties of Three Tri-nuclear Copper Clusters Based on Wells-Dawson Polyoxometalate

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.