Anion-Directed Self-Assembly of Coordination Polymer into Tunable Secondary Structure

A bent-shaped bipyridine ligand containing a dendritic aliphatic side chain has been synthesized as a ligand and complexed with silver ion through a self-assembling process. The resulting complexes were observed to self-assemble into supramolecular structures that differ significantly as a function of the counteranion size in the solid state, as confirmed by 1-D and 2-D X-ray diffraction experiments. The secondary structure of a cationic coordination chain appears to be dependent on the size of the counteranion. As the size of anion increases, the secondary structure of the coordination chain changes, from a helical chain, via a dimeric cycle, to a zigzag chain in the solid state. Interestingly, dilute solutions of the complexes exhibiting a columnar structure in polar solvents undergo spontaneous gelation and the resulting gels display a significant Cotton effect in the chromophore of the aromatic unit. These results represent a significant example that small variation in the anion size can provide a useful strategy to manipulate the secondary structure of linear chain and thereby solid-state supramolecular structure.