New 3-D polyoxovanadoborate architectures based on [V12B18O60](16-) clusters

作者：Zhou, Jian^*; Liu, Xing; Chen, Rong; Xiao, Hong-Ping; Hu, Feilong; Zou, Huahong; Zhou, Yun; Liu, Chun; Zhu, Ligang

来源：CrystEngComm, 2013, 15(25): 5057-5063.

DOI：10.1039/c3ce40428e

• HYDROTHERMAL SYNTHESIS
• CRYSTAL-STRUCTURE
• BORATE
• UNITS
• POLYOXOMETALATE
• VANADOBORATE
• SPECTROSCOPY
• SYSTEM
• SERIES
• CHAIN

Three new 3-D polyoxovanadoborates {[Cu(dien)(H2O)](3)V12B18O54(OH)(6)(H2O)}center dot 4H(3)O center dot 5.5H(2)O (1, dien = diethylenetriamine), {[Cd(H2O)(2)](3)V12B18O54(OH)(6)(H2O)}center dot 4H(3)O center dot 9.5H(2)O (2) and {[Na(H2O)(3)](4)Na2V12B18O56(OH)(4)(H2O)}(H(3)dien)(2) (3) have been hydrothermally synthesized and structurally characterized. Compounds 1-3 contain vanadoborate cluster [V12B18O60] constructed by two hexameric oxovanadate units [V6O9] and one puckered [B18O42] ring via sharing O atoms. The vanadoborate cage [V12B18O60] can present different degrees of protonation, namely [V12B18O60H6](10-) for 1 and 2, [V12B18O60H4](12-) for 3. The clusters [V12B18O60H6](10-) in 1 are connected by complex cations [Cu(dien)(H2O)](2+) into a new 3-D framework via all terminal O atoms of square-pyramidal [VO5] groups, while the clusters [V12B18O60H6](10-)/[V12B18O60H4](12-) in 2 and 3 are linked with [Cd(H2O)(2)](2+) groups/the combination of [Na(H2O)(3)](+) and Na+ ions to give another two types of new 3-D frameworks via O atoms of [BOx] (x = 3, 4) polyhedra, respectively. Magnetic measurements illustrate that compounds 1 and 2 have antiferromagnetic exchange interactions between metal centers. The theoretical band structure of 2 has been also studied.

• 出版日期2013
• 单位广西师范大学; 重庆师范大学; 玉林师范学院; 温州大学