Supramolecular Alloys from Fluorinated Hybrid Tri(4)Di(6) Imine Cages

To create innovative materials, efficient control and engineering of pore sizes and their characteristics, crystallinity and stability is required. Eight hybrid Tri(4)Di(6) imine cages with a tunable degree of fluorination and one fully fluorinated Tri(4)Di(6) imine cage are investigated. Although the fluorinated and the non‐fluorinated building blocks used herein differ vastly in reactivity, it was possible to gain control over the outcome of the self‐assembly process, by carefully controlling the feed ratio. This represents the first hybrid material based on fluorinated/hydrogenated porous organic cages (POCs). These cages with unlimited miscibility in the solid state were obtained as highly crystalline samples after recrystallization and even showed retention of the crystal lattice, forming alloys. All mixtures and the fully fluorinated Tri(4)Di(6) imine cage were analyzed by MALDI‐MS, single‐crystal XRD, powder XRD and in regard to thermal stability (TGA).