Periphery-substituted [4+6] salicylbisimine cage compounds with exceptionally high surface areas: Influence of the molecular structure on nitrogen sorption properties

摘要

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 m ~2g ~(-1) for all cage compounds 3c-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 m ~2g ~(-1) (for cage compound 3c with methyl substituents), 309 m ~2g ~(-1) (for cage compound 3d with 2-(2-ethyl-pentyl) substituents) and 22 m ~2g ~(-1) (for cage compound 3e with trityl substituents). Furthermore, we found that two different crystalline polymorphs of the cage compound 3a (with tert-butyl substituents) differ also in nitrogen sorption, resulting in a BET surface area of 1377 m ~2g ~(-1), when synthesized from THF and 2071 m ~2g ~(-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 m ~2g ~(-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 m ~2g ~(-1)!