A feasible route to approach 3D POM-based hybrids: utilizing substituted or reduced Keggin anions with high charge density

作者：Zhang, Chun-Jing; Pang, Hai-Jun; Tang, Qun; Chen, Ya-Guang^*

来源：Dalton Transactions, 2012, 41(31): 9365-9372.

DOI：10.1039/c2dt30152k

• HYDROTHERMAL SYNTHESIS
• CRYSTAL-STRUCTURE
• POLYOXOMETALATE CLUSTERS
• COORDINATION POLYMERS
• STRUCTURAL-CHARACTERIZATION
• COMPLEXES
• UNITS
• HETEROPOLYTUNGSTATES
• ASSEMBLIES
• OXIDATION

Five new hybrid compounds based on Keggin polyanions, Ag+/Cu+ ions and 1,3-bis(1,2,4-triazol-1-yl)-propane (btp) molecules have been hydrothermally synthesized. In [Ag-5(btp)(4)(H2O)(2)][PCuW11O39]center dot 2H(2)O (1), [Ag4.33Na0.67(btp)(4)(H2O)(2)][PMnMo11O39]center dot H2O (2) and [Cu-4(btp)(4)Na(H2O)(2)][PMnMo11O39]center dot 2H(2)O (3), the neighboring mono-substituted Keggin clusters are alternately connected via sharing oxygen atoms to form an unusual Keggin-based transition-metal monosubstituted chain, in which the Keggin cluster serves as a decadentate ligand and grafts ten metal atoms representing the highest connected number for Keggin cluster and forming a 3D framework. In [Ag-5(btp)(4)][PWVI W-10(V) O-2(40)] (4) and [Ag-5(btp)(4)] [PMoVI Mo-10(V) O-2(40)] (5), two-electron reduced Keggin clusters as hexadentate linkages are inserted in the rhomboid-like tunnels of the Ag-btp framework and connect with the framework via six Ag-O bonds to achieve 3D motifs, which are new and rare examples of heteropoly blue based hybrid compounds. The successful synthesis of the five high-dimensional structures may provide a feasible route for us to approach 3D polyoxometalate-based hybrids by using substituted Keggin anions and heteropoly blues with high charge density. Furthermore, photocatalytic experiments indicate that both 1 and 4 have good activities for photocatalytic degradation of RhB under UV irradiation. The luminescent properties of compounds 1-5 in the solid state were also investigated.

• 出版日期2012
• 单位黑龙江中医药大学; 哈尔滨学院; 东北师范大学