Supramolecular polymerization of [6]helicene-based cyano-luminogens: on the overall efficiency of self-assembled...

The synthesis of the [6]helicene-based luminophores 1 and 2 is reported. These chiral systems, endowed with cyano-stilbene fragments, form supramolecular polymers by the operation of intermolecular H-bonding interactions between the amides present in the peripheral side chains. The dissimilar disubstitution of 1 and 2 plays a crucial role in their self-assembling features. Thus, 1 does not show an efficient π-stacking of the central aromatic moiety. Instead, its self-assembling process results in a zig-zag arrangement of the monomeric units to form the aggregated species. On the other hand, 2 presents an efficient overlap of the aromatic backbones that affords a co-facial arrangement of the monomeric units. The solvent-dependent studies indicate that both [6]helicenes self-assemble following a cooperative supramolecular polymerization mechanism with a higher degree of cooperativity and stability for compound 2. The enantioenriched samples of both 1 and 2 display a rich dichroic pattern that changes when the supramolecular polymerization takes place. Furthermore, the presence of the cyano-stilbene moieties gives rise to an aggregation induced emission effect. The inherent chirality of both the monomeric and aggregated species of 1 and 2 provides the systems with CPL-emitting properties, presenting a remarkable overall CPL-efficiency, quantified by the B_CPL parameter, that increases upon supramolecular polymerization.