Restricting the Shape-Assisted Self-Assembly of Carpyridines to One Dimension
Shape-Assisted Self-Assembly (SASA) is a process in which the shape of a monomeric unit enforces the order between monomeric units needed for supramolecular assemblies in the absence of strong non-covalent interactions such as H-bonding.1-3 Saddle-shaped molecules stand out for these processes due to the translational and rotational rigidity of the monomers within the stacks. Carpyridines (CPs) are porphyrin-related metal-containing macrocycles bearing two carbazole and two pyridine units alternately connected through ortho aryl-aryl bonds.1,2 This arrangement results in a saddle-shaped structure, where prefunctionalized building blocks allow the synthesis and tuning of properties of these macrocycles. These units have shown to be effective towards supramolecular assembly purely based on p-p interactions and assisted by the shape of the monomers, demonstrating the significance of shape in self-assembly processes. Alkyl substitution onto the carbazoles has allowed us to study 2D sheet formation,1,2 which combined with substitution onto the pyridines with different side chains allows us to study the mechanism of assembly of the monomers into oligomers, and ultimately, into micrometer-long fibers.4
[1] Joseph F. Woods, Lucía Gallego, Pauline Pfister, Mounir Maaloum, Andreas Vargas Jentzsch, Michel Rickhaus, Nat. Commun., 2022, 13, 3681.
[2] Joseph F. Woods, Lucía Gallego, Amira Maisch, Dominik Renggli, Corrado Cuocci, Olivier Blacque, Gunther Steinfeld, Andres Kaech, Bernhard Spingler, Andreas Vargas Jentzsch, Michel Rickhaus, ChemRxiv 2023. https://doi.org/10.26434/chemrxiv-2023-whjkw.
[3] Lucía Gallego, Joseph F. Woods, Michel Rickhaus, M. Organic Materials, 2022, 4, 137–145.
[4] Lucía Gallego, Joseph F. Woods, Rachele Butti, Piotr Szwedziak, Andreas Vargas Jentzsch, Michel Rickhaus, under review.