Photoresponsive Dissipative Macrocycles Using Visible-Light-Switchable Azobenzenes

Visible light can be used to shift dynamic covalent imine assemblies out of equilibrium. We studied a fluorinated azobenzene building block that reliably undergoes geometric isomerism upon irradiation. The building block was used in combination with two different amines, ethylenediamine and R,R-1,2-diaminocyclohexane, to create a library of imine macrocycles. Whereas the simple amine can be used to access a polymeric state and a defined bowl-shaped macrocycle, the chiral amine gives access to a rich network of macrocycles that undergo both isomerisation as well as interconversion between different macrocyclic species, thereby allowing for control over the number of monomers involved in the cyclo-oligomerization; ¹ H- and ¹⁹ F-DOSY NMR, MALDI-MS measurements, and UV/Vis spectroscopy were used to study the processes.