Supramolecular Alloys from Fluorinated Hybrid Tri⁴Di⁶Imine Cages

Abstract

To create innovative materials, efficient control and engineering of pore sizes and their characteristics, crystallinity and stability is required. Eight hybrid Tri4Di6 imine cages with a tunable degree of fluorination and one fully fluorinated Tri4Di6 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 Tri4Di6 imine cage were analyzed by MALDI‐MS, single‐crystal XRD, powder XRD and in regard to thermal stability (TGA).

Fluorine‐Boosted Kinetic and Selective Molecular Sieving of C6 Derivatives

“…From a design perspective, improving hydrophobicity of the sieving platform can improve the kinetics of hydrocarbon separation. This has been verified in organic cages and MOFs where using fluorine improved not only hydrophobicity but also thermal stability [37–45] . Herein, an adaptive porous fluorinated leaning pillararene was synthesized with persistent porosity and was efficiently employed to separate benzene traces after catalytic hydrogenation to produce high purity cyclohexane under dynamic conditions (Figure 1).…”

“…This has been verified in organic cages and MOFs where using fluorine improved not only hydrophobicity but also thermal stability. [37][38][39][40][41][42][43][44][45] Herein, an adaptive porous fluorinated leaning pillararene was synthesized with persistent porosity and was efficiently employed to separate benzene traces after catalytic hydrogenation to produce high purity cyclohexane under dynamic conditions (Figure 1). This fluorinated molecular sieving platform showed a relatively fast adsorption, which was comparable to MOFs with high selectivity and reproducibility.…”

Porous Organic Compounds – Small Pores on the Rise

“…After recrystallization, these cages with unlimited miscibility in the solid‐state were obtained as highly crystalline samples that even retained the crystal lattice, forming alloys. They remained essentially nonporous although huge voids are present in the structure, because they are not interconnected, 0D pores [18] …”

“…They remained essentially nonporous although huge voids are present in the structure, because they are not interconnected, 0D pores. [18] A series of three rylene-type cages were investigated by the group of Šolomek, also extending the repertoire of POCs towards photochemistry (Figure 7). [19] The incorporated rylene diimides are not only interesting because of their strong adsorption and emission but they are also potent electron acceptors with favorable redox potentials.…”

Design of aD3h-symmetry prismatic tris-(ferrocene-1,1′-diyl) molecular cage bearing boronate ester linkages

“…13 Alternatively, it was demonstrated that discrete organic cages could be synthesized instead of COFs using different starting materials that induce the 3D geometry. [14][15][16][17] Such cages are commonly porous organic materials. Their synthesis usually employs imine bond formations, based on the reaction between amine and aldehyde components.…”