Silver(I) arylsulfonates: a systematic study of "softer" hybrid inorganic-organic solids.
The present study represents the first systematic examination of the effects on the layered structure of simple silver aryl-monosulfonates as the breadth of the pendant aryl group is increased beyond that where a simple "phosphonate-like" motif is sustainable. Five new silver arenesulfonates are reported. On the basis of comparison with Ag benzenesulfonate, a threshold of approximately 6.4 A is proposed and confirmed as the critical breadth of an aryl group for a simple layered motif to be observed in silver sulfonates. Ag 1,1'-biphenyl-4-sulfonate (1) and Ag 2-naphthalenesulfonate (2) are below this threshold and so form simple layered networks, termed type 1 solids. When the pendant group is broadened to a 1-naphthyl group, the layer incorporates coordinated water to maintain a layered structure giving Ag 1-naphthalenesulfonate hemihydrate (3a). This more diffuse structure is termed a type 2 solid. For anhydrous Ag 1-naphthalenesulfonate (3) and Ag 1-pyrenesulfonate (4), the additional breadth is compensated for by the formation of Ag-pi interactions and the formation of type 3 solids. Interactions between the pendant groups are observed to play a significant role in the packing of the solid. All frameworks are characterized by single crystal and powder X-ray diffraction, IR, DSC-TGA, and elemental analysis. The significance of this adaptable framework is discussed along with implications for design of stacked arene arrays.
Department of Chemistry, University of Calgary, Calgary, Alberta T2N 1N4, Canada.
Adrien P
AP
Côté
George K H
GK
Shimizu