Atomic observation and structural evolution of covalent organic framework rotamers

• 成果类型: Article
• 署名作者: Zeng, Tengwu; Ling, Yang; Jiang, Wentao; Yao, Xuan; Tao, Yu; Liu, Shan; Liu, Huiyu; Yang, Tieying; Wen, Wen; Jiang, Shan; Zhao, Yingbo; Ma, Yanhang; Zhang, Yue - Biao
• 署名单位: ShanghaiTech University; ShanghaiTech University; Chinese Academy of Sciences; Shanghai Advanced Research Institute, CAS; ShanghaiTech University
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-14470
• DOI: 10.1073/pnas.2320237121
• 发表日期: 2024-01-30
• 关键词: design; methane; storage

摘要

Dynamic 3D covalent organic frameworks (COFs) have shown concerted structural transformation and adaptive gas adsorption due to the conformational diversity of organic linkers. However, the isolation and observation of COF rotamers constitute undergoing challenges due to their comparable free energy and subtle rotational energy barrier. Here, we report the atomic-level observation and structural evolution of COF rotamers by cryo-3D electron diffraction and synchrotron powder X-ray diffraction. Specifically, we optimize the crystallinity and morphology of COF-320 to manifest its coherent dynamic responses upon adaptive inclusion of guest molecules. We observe a significant crystal expansion of 29 vol% upon hydration and a giant swelling with volume change up to 78 vol% upon solvation. We record the structural evolution from a non- porous contracted phase to two narrow-pore intermediate phases and the fully opened expanded phase using n-butane as a stabilizing probe at ambient conditions. We uncover the rotational freedom of biphenylene giving rise to significant conformational changes on the diimine motifs from synclinalto syn-periplanar and anticlinalrotamers. We illustrate the 10-fold increment of pore volumes and 100% enhancement of methane uptake capacity of COF-320 at 100 bar and 298 K. The present findings shed light on the design of smarter organic porous materials to maximize host-guest interaction and boost gas uptake capacity through progressive structural transformation.