We report the first POC, containing perfluorinated aromatic panels forming quickly and in high purity, despite low preorganization encoded in the starting materials.

Herein, we report the synthesis and crystal structures of three [2+2] supramolecular boxes assembled by halogen bonding.

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; 1H‐ and 19F‐DOSY NMR, MALDI‐MS measurements, and UV/Vis spectroscopy were used to study the processes.

ortho-Fluoroazobenzenes are a remarkable example of bistable photoswitches, addressable by visible light. Symmetrical, highly fluorinated azobenzenes bearing an iodine substituent in para-position were shown to be suitable supramolecular building blocks both in solution and in the solid state in combination with neutral halogen bonding acceptors, such as lutidines. Therefore, we investigate the photochemistry of a series of azobenzene photoswitches. Upon introduction of iodoethynyl groups, the halogen bonding donor properties are significantly strengthened in solution. However, the bathochromic shift of the π→π* band leads to a partial overlap with the n→π* band, making it slightly more difficult to address. The introduction of iodine substituents is furthermore accompanied with a diminishing thermal half-life. A series of three azobenzenes with different halogen bonding donor properties are discussed in relation to their changing photophysical properties, rationalized by DFT calculations.

Halogen bonding of neutral donors using imine groups of porous organic cage compounds as acceptors leads to the formation of halogen-bonded frameworks. We report the use of two different imine...

Mit sichtbarem Licht lassen sich dynamische, kovalente Iminverbindungen aus dem Gleichgewicht bringen. Wir haben einen fluorierten Azobenzol‐Baustein untersucht, der bei Bestrahlung zuverlässig eine geometrische Isomerie eingeht. Der Baustein wurde in Kombination mit zwei verschiedenen Aminen, Ethylendiamin und R,R‐1,2‐Diaminocyclohexan, verwendet, um eine Bibliothek von Imin‐Makrocyclen zu erstellen. Während mit dem einfachen Amin ein polymerer Zustand und ein definierter schalenförmiger Makrocyclus erhalten werden kann, ermöglicht das chirale Amin den Zugang zu einem großen Netzwerk von Makrocyclen, die sowohl eine Isomerisierung als auch eine Interkonversion zwischen verschiedenen makrocyclischen Spezies durchlaufen, wodurch die Anzahl der an der Cyclo‐Oligomerisierung beteiligten Monomere kontrolliert werden kann. Diese Prozesse wurden mittels 1H‐ und 19F‐DOSY NMR, MALDI‐MS‐Messungen und UV/Vis‐Spektroskopie untersucht.

We recently communicated photoresponsive, dissipative, and dynamic covalent macrocycles using visible light photoswitching. Several exciting contributions using metal-organic and metal-free supramolecular assemblies were published back-to-back, and we have a closer look at these contributions together with an in-depth insight into our macrocyclic system.