Molecular containers Macrocycles, cages and photocages

This thesis explores the design and properties of molecular containers for the controlled storage and release of molecules, focusing on three key classes: supramolecular tubes assembled from macrocycles, porous organic cages, and photocages. The first part investigates supramolecular nanotubes formed from macrocyclic building blocks, where the balance between hydrogen bonding and halogen interactions governs tubular assembly in single crystals. A key insight is the substitution of bromines with iodines, which strengthens halogen bonding and enhances structural integrity. The study then turns to rylene diimide based organic cages, with a focus on reducing their symmetry to increase functional diversity. Using principles of dynamic covalent chemistry and self-sorting, the formation of kinetically trapped cages is examined, revealing how subtle changes in reaction conditions affect stability and selectivity. The kinetic formation of rylene diimide cages is leveraged to identify intermediates formed during cage assembly and to propose a detailed formation mechanism. Two intermediates were successfully isolated, characterized, and evaluated regarding their kinetic stability. Finally, the isolated intermediates were transformed into cages with reduced symmetry, resulting in varying selectivity. Notably, one case demonstrated the clean formation of a heteroleptic cage. Lastly, the thesis explores bodipy-based photocages as light-responsive molecular tools. These enable selective labeling and cleavage of biomolecules upon green light irradiation, offering a method to control charge states in high-vacuum environments. Computational and experimental studies elucidate the photochemical mechanisms, demonstrating the potential of photocages in precision molecular manipulation.