One-dimensionally (1D) elongated molecular assemblies with high degrees of internal order1, categorized as supramolecular polymers (SPs) (ref. 2), represent emerging stimuli-responsive materials with interesting functions and properties3,4,5,6,7,8. A variety of functional SPs have been developed, while precise supramolecular polymerization has been devised recently, which is inspired by the biological system as well as synthetic polymers9,10. An important issue that has not yet been addressed in the context of SPs is dynamic control over their higher-order structures at the nanoscale (for example, helical coils), despite the fact that typical helical columnar structures at the primary level11,12,13,14,15 have been well studied in terms of internal order. Changes in the higher-order conformation of biopolymers play an important role in biological systems, which is arguably best reflected in protein folding16. For instance, folded proteins are functional, whereas unfolded/misfolded proteins generally lose their functionality. Inspired by these naturally occurring polymers, the control over folding has been explored in synthetic covalent polymers17,18,19,20,21,22 and oligomers21,23,24,25,26, which are referred to as foldamers21,27,28,29. In order to mimic the functions of biopolymers and/or compete with oligomeric as well as polymeric foldamers, remote control over the conformation of the SP backbone is required.

To address this issue, herein, we have used a previously reported barbiturated naphthalene derivative, which polymerizes non-covalently into uniform toroidal nanostructures via stacking of hydrogen-bonded hexamers30,31. The introduction of a photoresponsive azobenzene into the parent-barbiturated naphthalene results in increased attractive forces between the stacking molecules, and causes T5 Fluorescent Lamp-induced changes of the molecular shape32,33,34,35,36. Depending on the polymerization conditions, the new molecule non-covalently polymerizes into various quasi 1D structures with spontaneous curvature, ranging from randomly coiled to helically folded fibres. Photoisomerization of the azobenzene unit by exposure to ultraviolet (UV) or visible (Vis) light provides a means to reversibly destroy or recover the curvature of the main chain, respectively. Thus, an external dynamic control over helical secondary structures of SPs is demonstrated. Although the terminologies conformation and folding/unfolding are commonly reserved for covalent polymer chains, we are using them here in the context of non-covalent polymer chains to illustrate the conceptual similarity.