Designing extrinsic porosity in supramolecular organic frameworks: Structural control with giant tetrahedral molecules

Creating stable and well‐defined porosity in supramolecular structures is a significant challenge due to the sensitivity of non‐covalent interactions to environmental conditions. This study addresses this challenge by exploring the design and synthesis of extrinsic porous materials using giant tetrahedral molecules as fundamental building blocks within supramolecular frameworks. By incorporating multi‐armed pyrene derivatives (Py x ) into a self‐assembly system with a rigid giant tetrahedral molecule (tetraNDI), the charge‐transfer (CT) interaction was utilized to guide the construction of robust supramolecular architectures. The geometric interplay between tetraNDI and the Py x derivatives was found to be pivotal in determining the final structural forms, as the Py 4 and Py 3 interlock with tetraNDI to form a 1D columnar phase, whereas the Py 2 caps tetraNDI to form a 2D lamellar phase. Stable and precise molecular‐level vacancies were identified in the porous supramolecular columns of tetraNDI:Py 3 by in situ temperature‐dependent wide‐angle X‐ray scattering (WAXS) and thermal analysis. The findings not only extend our understanding of supramolecular chemistry but also offer a novel approach to the strategic design of porous materials, addressing the fundamental issue of environmental sensitivity in non‐covalently bonded structures.