Construction of Ag/1,2,4-Triazole/Polyoxometalates Hybrid Family Varying from Diverse Supramolecular Assemblies to 3-D Rod-Packing Framework
详细信息 查看全文
- 作者：Quan-Guo Zhai ; Xiao-Yuan Wu ; Shu-Mei Chen ; Zhen-Guo Zhao ; Can-Zhong Lu
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：June 11, 2007
- 年：2007
- 卷：46
- 期：12
- 页码：5046 - 5058
- 全文大小：649K
- 年卷期：v.46,no.12(June 11, 2007)
- ISSN：1520-510X
文摘
Eight members of the Ag/1,2,4-triazole/polyoxometalates (POMs) hybrid supramolecular family, namely, [Ag4(dmtrz)4][Mo8O26] (dmtrz = 3,5-dimethyl-1,2,4-triazole, 1), [Ag6(3atrz)6][PMo12O40]2·H2O (3atrz = 3-amino-1,2,4-triazole, 2),[Ag2(3atrz)2]2[HPMoVI10MoV2O40] (3), [Ag2(dmtrz)2]2[HPMoVI10MoV2O40] (4), [Ag2(trz)2]2[Mo8O26] (trz = 1,2,4-triazole,5), [Ag2(3atrz)2][Ag2(3atrz)2(Mo8O26)] (6), [Ag4(4atrz)2Cl][Ag(Mo8O26)] (4atrz = 4-amino-1,2,4-triazole, 7), and [Ag5(trz)4]2[Ag2(Mo8O26)]·4H2O (8), were synthesized through hydrothermal reactions of 1,2,4-triazole or its derivativeswith appropriate silver salts and molybdates. Crystal structure analysis reveals that the POM-dependent Ag-1,2,4-triazolate units in these hybrid compounds form a novel tetranuclear cluster (1), a unique double calix[3]arene-shaped hexamer (2), zigzag chains (5 and 6), helix chains (3, 4, and 8), and an interesting looped chain (7). Aseries of hydrogen bonding-based supramolecular assemblies varying among the 0-D + 0-D (1 and 2), 0-D + 1-D(3 and 4), 1-D + 1-D (5 and 7), and 1-D + 2-D (6) modes between the organomatic cations and POM anions wereobserved in these structures. Moreover, the inorganic chain [Ag(Mo8O26)]n3n- in 7 constructed by the building block[Mo8O26]4- linked only via single Ag+ ion is unprecedented. Compound 8 is the first high-dimensional frameworkconstructed from the [Ag2(Mo8O26)]n2n- rod-shaped subunits. These hybrid supramolecular compounds presentinteresting photochemical properties. The spectroscopic experiments show that they not only are potentialsemiconductor materials but also have interesting photoluminescence phenomena, including O 
Mo [LMCT] andintraligand [
- *] emissions generated by internal heavy metal effect.
Mo [LMCT] andintraligand [ - *] emissions generated by internal heavy metal effect.