Varying the extended packing of silver(I) ladder-like coordination polymers by modifying the organic group of various organosulfonate anions

The ability to reliably produce one-dimensional ladder-like coordination polymers that display different crystal packing has been realized. These ladder polymers are produced by incorporating 4,4′-azopyridine (4,4-Azo) molecules as the bridging ligand that act as the stiles or rods for the ladder. The rungs are based upon silver dimers that interact by means of argentophilic forces which were formed with the assistance of the sulfonate anion. Due to the selection of various organosulfonate anions, namely p-toluenesulfonate, trifluoromethanesulfonate, and methanesulfonate, the ability to vary the R-group serves as an easy component to fine tune the overall packing of the polymeric material. The various polymeric structures and their packing will be discussed with special attention to silver–silver distances not only within the ladder but also between nearest neighbor chains. In addition, the change in occupancy of the bridging 4,4-Azo as a function of temperature will be address as this is indicative of pedal motion within the crystal lattice. Lastly, hydrogen bonding patterns in each will also be discussed as a means to produce multi-dimensional frameworks beyond the ladder-like chain.

The ability to reliably produce one-dimensional ladder-like coordination polymers based upon 4,4′-azopyridine has been realized that display different crystal packing due to the shape of the organosulfonate anions. The anions employed were based upon p-toluenesulfonate, trifluoromethanesulfonate, and methanesulfonate where varying the R-group fine tunes the overall packing of the ladders.Figure optionsDownload as PowerPoint slide