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.