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Inorg Chem. 2007 Jun 11;46(12):5046-58. Epub 2007 May 8.

Construction of Ag/1,2,4-triazole/polyoxometalates hybrid family varying from diverse supramolecular assemblies to 3-d Rod-packing framework.

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  • 1State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P. R. China.

Abstract

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 derivatives with 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). A series 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 were observed 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 framework constructed from the [Ag2(Mo8O26)]n2n- rod-shaped subunits. These hybrid supramolecular compounds present interesting photochemical properties. The spectroscopic experiments show that they not only are potential semiconductor materials but also have interesting photoluminescence phenomena, including O-->Mo [LMCT] and intraligand [pi-pi*] emissions generated by internal heavy metal effect.

PMID:
17487968
[PubMed]
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