Chiral versus Achiral Assemblies in Multi-Stimuli Responsive Supramolecular Polymerization of Tetra-Substituted Azobenzene Dye

Incorporating photoswitchable moieties into the molecular design of supramolecular architectures provides unique opportunities for controlling their morphology and functionality via optical stimuli. Harnessing geometrical and electrical changes in response to multiple external stimuli on the molecular level to modulate properties remains a fundamental challenge. Herein, the reversible formation of the aggregates of l-tyrosine E-azobenzene-tetracarboxamide (E-ABT) is shown to be finely controlled by light, solvent, or chemical additives. The resulting products differ not only in their overall morphology and supramolecular interactions, but also in their intrinsic chirality, that is, depending on the conditions applied, self-assembly yields chiral columns or pi-stacked "achiral" oligomers. This report shows the potential of rational monomer design to achieve controlled self-assembly by stimuli of choice and paves the way toward the use of multi-responsive, sterically hindered azo-benzene aggregates in materials chemistry and nanotechnology. Herein, the non-covalent self-assembly of an amino-acid substituted azobenzene dye in solution and the solid state is presented. Depending on the conditions applied, the process yields chiral columns or pi-stacked "achiral" oligomers in the ground state and might be further altered by external stimuli such as light, solvent, or chemical additives. image