Supramolecular coordination cages show a wide range of useful properties including, but not limited to, complex molecular machine-like operations, confined space catalysis, and rich host-guest chemistries. Here we report the uptake and release of non-covalently encapsulated, pharmaceutically-active cargo from an octahedral Pd cage bearing polymer chains on each vertex. Six poly(ethylene glycol)decorated bipyridine ligands are used to assemble an octahedral Pd II 6 (TPT) 4 cage. The supramolecular container encapsulates progesterone and ibuprofen within its hydrophobic nanocavity and is activated by shear force produced by ultrasonication in aqueous solution entailing complete cargo release upon rupture, as shown by NMR and GPC analyses.

Porous materials are important for various energy‐related technologies such as catalysis and separation. While porous organic cage compounds are a rather recent addition to the field of porous materials, these discrete nanocavities have since emerged as a versatile functional‐materials platform, facilitated by the solubility of the materials in common organic solvents. In contrast to other frameworks, organic cages are assembled first from modular building blocks in solution and then packed in the solid‐state in a next step. In this minireview, we highlight examples of porous organic cages with focus on how the intrinsic nanopore can be controlled and utilized, especially focusing on their synthesis and the gas sorption properties of smaller intrinsic pores of porous organic cage compounds, porous macrocycles, and other related compounds.

In a two-step synthesis, a novel highly fluorinated dialdehyde is accessible. This very reactive building block for dynamic imine chemistry is exemplarily utilized in a condensation reaction to generate the first extensively fluorinated trianglimine. The analysis of the material properties and especially the crystal structure of the [3+3] macrocycle reveal a supramolecular organic framework with tubular porous channels. The use of fluorinated ligands to generate hydrophobic, electron-deficient channel-like pores is an important addition to the ever-expanding field of supramolecular networks and trianglimine chemistry in general.

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).

A simple, solvent-free synthetic protocol towards the synthesis of organic self-assembled macromolecules has been established. By employing mechanochemistry using glassware readily available to every organic chemist, we were able to...