Physical Chemistry Chemical Physics, 2016, vol 18, 30, pp. 20399-20409
Stimulus-responsive molecular gel systems, based on metal salts of a luminescent gelator, 9,10-dioxooctadecanoic acid (DODA), are reported. These salts are structurally the simplest metallo-gelators of which we are aware that exhibit controllable mechano-responsive and luminescent properties. Aggregation is more favored by the metal salts than for DODA itself. However, gelation ability differs dramatically depending on the metal ion: whereas the salts with zinc(II) and calcium(II) are inefficient gelators, those with nickel(II) and copper(II) can gelate various aromatic liquids, alkanes, and long-chained alcohols. Unlike the DODA gels, no aggregation-induced shift in the positions of the emission spectra of the metal salts could be observed as the sols were transformed to their gel phases. Gels of both nickel(II) and copper(II) salts in benzonitrile are among the few known examples with crystalline networks and exhibiting thixotropic behavior. However, there are significant differences in their abilities to recover the initial viscoelastic properties. Structural data for the solid and gel states lead us to conclude that differences among the gelating abilities can be attributed principally to the specific nature of interactions of the salts at their head groups. They appear to control the mechanical and emissive properties of the gels as well as whether the initial aggregation of the salts in the sol phases will support the growth of 1D objects that are capable of maintaining strong contacts, leading to 3D networks and gel formation. Overall, the results provide a facile strategy for the design of luminescent materials with controllable mechano-responsiveness by modifying the metal ions within fibrillar assemblies.