posted on 2013-09-23, 00:00authored byLi-Li Wen, Han Wang, Chong-Qing Wan, Thomas C. W. Mak
Five
new silver(I)–organic frameworks containing ethynediide or
alkyl and aryl ethynide, together with newly designed oligo-α-sulfanylpyrazinyl
ligands, namely, [(Ag2C2)2(AgCF3COO)11(L1)(μ2-DMSO)3(DMSO)5]·1/4H2O (L1 = 2,6-bis(pyridin-2-ylthio)pyrazine, 1), [(Ag2C2)2(AgCF3COO)11(L2)(μ2-DMSO)5(DMSO)3]·1/4H2O (L2 = 2-(pyrazin-2-ylthio)-6-(pyridin-2-ylthio)pyrazine, 2), [(AgCCtBu)2(AgCF3COO)5(L3)(DMSO)3(H2O)] (L3 = 2,6-bis(pyrazin-2-ylthio)pyrazine, 3), [(AgCCPh)4(AgCF3COO)2(L3)(DMSO)2]·DMSO·1/2H2O (4), and [(AgCCC6H4Cl-3)4(AgCF3COO)2(L3)(DMSO)]·H2O (5), have been synthesized and characterized by X-ray
crystallography. Isomorphous complexes 1 and 2 feature an infinite coordination chain composed of (C2)2Ag15 clusters alternatively linked by L1 or L2 ligands; weak intermolecular C–H···F
hydrogen bonding between adjacent infinite chains results in a three-dimensional
supramolecular network. Complex 3 exhibits a coordination
layer structure composed of (tBuC2)2Ag7 aggregates. Compounds 4 and 5 are nearly isostructural, each possessing a ladder-like
chain with a centrosymmetric (arylC2)8Ag12 cluster as its structure building unit. With the assistance
of weak intermolecular hydrogen bonds, three-dimensional and two-dimensional
supramolecular architectures were generated in 4 and 5, respectively. The diverse coordination modes of oligo-α-sulfanylpyrazinyl
ligands Ln (n = 1, 2,
3) account for the variable framework dimensionalities observed for 1–5. Notably, complexes 3–5 provide the first examples of extended, conformationally
flexible N-donor ancillary ligands incorporated into silver alkyl
and aryl ethynide systems. In addition, complexes 1–5 display ligand-based photoluminescence.