Periphery-Substituted [4+6] Salicylbisimine Cage Compounds with Exceptionally High Surface Areas: Influence of the Molecular Structure on Nitrogen Sorption Properties

The synthesis of various periphery‐substituted shape‐persistent cage compounds by twelve‐fold condensation reactions of four triptycene triamines and six salicyldialdehydes is described, where the substituents systematically vary in bulkiness. The resulting cage compounds were studied as permanent porous material by nitrogen sorption measurements. When the material is amorphous, the steric demand of the cages exterior does not strongly influence the gas uptake, resulting in BET surface areas of approximately 700 m2 g−1 for all cage compounds 3 c–e, independently of the substituents bulkiness. In the crystalline state, materials of the same compounds show a strong interconnection between steric demand of the peripheral substituent and the resulting BET surface area. With increasing bulkiness, the overall BET surface area decreases, for example 1291 m2 g−1 (for cage compound 3 c with methyl substituents), 309 m2 g−1 (for cage compound 3 d with 2‐(2‐ethyl‐pentyl) substituents) and 22 m2 g−1 (for cage compound 3 e with trityl substituents). Furthermore, we found that two different crystalline polymorphs of the cage compound 3 a (with tert‐butyl substituents) differ also in nitrogen sorption, resulting in a BET surface area of 1377 m2g−1, when synthesized from THF and 2071 m2g−1, when recrystallized from DMSO. Amorphous versus crystalline: Shape‐persistent organic cage compounds (see scheme) with equal defined cavities, but different peripheral substituents, show permanent porosities in the solid state. If the materials are amorphous, the peripheral substituents do not influence the sorption of nitrogen, resulting in BET surface areas of approximately 700 m2g−1, independent of the substituent bulkiness. In the crystalline state, the less bulky the substituents the higher the specific BET surface area, ranging from 22 up to 2071 m2 g−1!