Isoreticular Crystallization of Highly Porous Cubic Covalent Organic Cage Compounds

Modular frameworks featuring well‐defined pore structures in microscale domains establish tailor‐made porous materials. For open molecular solids however, maintaining long‐range order after desolvation is inherently challenging, since packing is usually governed by only a few supramolecular interactions. Here we report on two series of nanocubes obtained by co‐condensation of two different hexahydroxy tribenzotriquinacenes (TBTQs) and benzene‐1,4‐diboronic acids (BDBAs) with varying linear alkyl chains in 2,5‐position. n‐Butyl groups at the apical position of the TBTQ vertices yielded soluble model compounds, which were analyzed by mass spectrometry and NMR spectroscopy. In contrast, methyl‐substituted cages spontaneously crystallized as isostructural and highly porous solids with BET surface areas and pore volumes of up to 3426 m2 g−1 and 1.84 cm3 g−1. Single crystal X‐ray diffraction and sorption measurements revealed an intricate cubic arrangement of alternating micro‐ and mesopores in the range of 0.97–2.2 nm that are fine‐tuned by the alkyl substituents at the BDBA linker. Isoreticular porous materials are obtained after crystallization of cubic organic cages with varying alkyl chains at the edges. Nitrogen sorption measurements revealed exceptionally high surface areas up to 3426 m2 g−1 and pore volumes up to 1.84 cm3 g−1. The intricate three‐dimensional array of alternating intrinsic and extrinsic pores remains intact upon solvent removal and pore sizes are fine‐tuned by the alkyl substituents.