Photoregulated Supramolecular Polymerization through Halogen Bonding

Supramolecular polymers are able to change their structure, morphology and function in response to external stimuli. However, controlling the independence of stimuli‐responses in these systems is challenging. Herein, we exploit halogen bonding (XB) as a reversible network element to regulate the photoresponsive and adaptive behavior of supramolecular polymers. To this end, we have designed a system comprising an amphiphilic XB acceptor with the ability to self‐assemble in aqueous media (OPE‐Py) and a molecule with a dual photoresponsive and XB donor function [(E)‐Azo‐I]. OPE‐Py self‐assembles in aqueous media into supramolecular polymers, which transform into nanoparticle assemblies upon co‐assembly with (E)‐Azo‐I. Interestingly, a third type of assembly (2D sheets) is obtained if OPE‐Py is treated with (E)‐Azo‐I and exposed to photoirradiation. At ambient conditions, both nanoparticles and 2D sheets remain invariant over time. However, heating dissociates the XB interactions present in both assemblies, resulting in their transformation to the original fiber‐like morphology of OPE‐Py. Thus, breaking the communication between self‐assembly and the stimuli‐responses upon heating restores the original state of the system, drawing parallels to feedback loops in programming language. This work broadens the still limited scope of XB in solution assemblies and paves the way for multifunctional adaptive supramolecular systems.