Silver–Organic Frameworks Containing Ethynediide or Ethynide with Ancillary Oligo-α-sulfanylpyrazinyl and Dimethylsulfoxide Ligands
dataset
posted on 2013-09-23, 00:00 authored by Li-Li Wen, Han Wang, Chong-Qing Wan, Thomas C. W. MakFive
new silver(I)–organic frameworks containing ethynediide or
alkyl and aryl ethynide, together with newly designed oligo-α-sulfanylpyrazinyl
ligands, namely, [(Ag<sub>2</sub>C<sub>2</sub>)<sub>2</sub>(AgCF<sub>3</sub>COO)<sub>11</sub>(L<sub>1</sub>)(μ<sub>2</sub>-DMSO)<sub>3</sub>(DMSO)<sub>5</sub>]·<sup>1</sup>/<sub>4</sub>H<sub>2</sub>O (L<sub>1</sub> = 2,6-bis(pyridin-2-ylthio)pyrazine, <b>1</b>), [(Ag<sub>2</sub>C<sub>2</sub>)<sub>2</sub>(AgCF<sub>3</sub>COO)<sub>11</sub>(L<sub>2</sub>)(μ<sub>2</sub>-DMSO)<sub>5</sub>(DMSO)<sub>3</sub>]·<sup>1</sup>/<sub>4</sub>H<sub>2</sub>O (L<sub>2</sub> = 2-(pyrazin-2-ylthio)-6-(pyridin-2-ylthio)pyrazine, <b>2</b>), [(AgCC<sup><i>t</i></sup>Bu)<sub>2</sub>(AgCF<sub>3</sub>COO)<sub>5</sub>(L<sub>3</sub>)(DMSO)<sub>3</sub>(H<sub>2</sub>O)] (L<sub>3</sub> = 2,6-bis(pyrazin-2-ylthio)pyrazine, <b>3</b>), [(AgCCPh)<sub>4</sub>(AgCF<sub>3</sub>COO)<sub>2</sub>(L<sub>3</sub>)(DMSO)<sub>2</sub>]·DMSO·<sup>1</sup>/<sub>2</sub>H<sub>2</sub>O (<b>4</b>), and [(AgCCC<sub>6</sub>H<sub>4</sub>Cl-<i>3</i>)<sub>4</sub>(AgCF<sub>3</sub>COO)<sub>2</sub>(L<sub>3</sub>)(DMSO)]·H<sub>2</sub>O (<b>5</b>), have been synthesized and characterized by X-ray
crystallography. Isomorphous complexes <b>1</b> and <b>2</b> feature an infinite coordination chain composed of (C<sub>2</sub>)<sub>2</sub>Ag<sub>15</sub> clusters alternatively linked by L<sub>1</sub> or L<sub>2</sub> ligands; weak intermolecular C–H···F
hydrogen bonding between adjacent infinite chains results in a three-dimensional
supramolecular network. Complex <b>3</b> exhibits a coordination
layer structure composed of (<sup><i>t</i></sup>BuC<sub>2</sub>)<sub>2</sub>Ag<sub>7</sub> aggregates. Compounds <b>4</b> and <b>5</b> are nearly isostructural, each possessing a ladder-like
chain with a centrosymmetric (arylC<sub>2</sub>)<sub>8</sub>Ag<sub>12</sub> cluster as its structure building unit. With the assistance
of weak intermolecular hydrogen bonds, three-dimensional and two-dimensional
supramolecular architectures were generated in <b>4</b> and <b>5</b>, respectively. The diverse coordination modes of oligo-α-sulfanylpyrazinyl
ligands L<sub><i>n</i></sub> (<i>n</i> = 1, 2,
3) account for the variable framework dimensionalities observed for <b>1</b>–<b>5</b>. Notably, complexes <b>3</b>–<b>5</b> provide the first examples of extended, conformationally
flexible N-donor ancillary ligands incorporated into silver alkyl
and aryl ethynide systems. In addition, complexes <b>1</b>–<b>5</b> display ligand-based photoluminescence.
