Construction of Ag/1,2,4-Triazole/Polyoxometalates Hybrid Family Varying from Diverse Supramolecular Assemblies to 3-D Rod-Packing Framework

Citations Over TimeTop 1% of 2007 papers

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.

Related Papers

• → 4-(4-Chlorobenzylideneamino)-3-(1H-1,2,4-triazol-1-ylmethyl)-1H-1,2,4-triazole-5(4H)-thione(2005)2 cited
• → 4-(2-Fluorobenzylideneamino)-3-(1,2,4-triazol-4-ylmethyl)-1H-1,2,4-triazole-5(4H)-thione(2005)1 cited
• → Crystal Structure and DFT Studies of a Triazole Derivative: 4-(2-Hydrobenzylideneamino) -3-(1,2,4-triazol-4-yl-methyl) 1H-1,2,4-triazole-5 (4H)-thione(2007)1 cited
• → 4-(2-Hydroxybenzylideneamino)-3-(1H-1,2,4-triazol-1-ylmethyl)-1H-1,2,4-triazole-5(4H)-thione(2005)
• → 4-(3-Nitrobenzylideneamino)-3-(1H-1,2,4-triazol-1-ylmethyl)-1H-1,2,4-triazole-5(4H)-thione(2007)