Zhong, Bing‐XuanBing‐XuanZhongChen, Lian‐TungLian‐TungChenLo, Chia‐YunChia‐YunLoChang, Po‐YaPo‐YaChangChuang, Wei‐TsungWei‐TsungChuangCHIEN LUNG WANG2025-10-272025-10-272025-09-30https://scholars.lib.ntu.edu.tw/handle/123456789/733037Creating 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 (Pyx) 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 Pyx derivatives was found to be pivotal in determining the final structural forms, as the Py4 and Py3 interlock with tetraNDI to form a 1D columnar phase, whereas the Py2 caps tetraNDI to form a 2D lamellar phase. Stable and precise molecular-level vacancies were identified in the porous supramolecular columns of tetraNDI:Py3 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.encharge-transfer interactionextrinsic porosityself-assemblysupramolecular chemistrysupramolecular organic frameworks[SDGs]SDG3journal article10.1002/jccs.70108