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A Convenient Strategy for Designing a Soft Nanospace: An Atomic Exchange in a Ligand with Isostructural Frameworks

Author:
Ma, Yunsheng, Matsuda, Ryotaro, Sato, Hiroshi, Hijikata, Yuh, Li, Liangchun, Kusaka, Shinpei, Foo, Mawlin, Xue, Fengfeng, Akiyama, George, Yuan, Rongxin, Kitagawa, Susumu
Source:
Journal of the American Chemical Society 2015 v.137 no.50 pp. 15825-15832
ISSN:
1520-5126
Subject:
X-ray diffraction, acetylene, adsorbents, adsorption, carbon dioxide, coordination polymers, ligands
Abstract:
Direct observation of gas molecules confined in the nanospace of porous materials by single-crystal X-ray diffraction (SXRD) technique is significant because it leads to deep insight into the adsorption mechanism and the actual state of the adsorbents in molecular level. A recent study revealed that flexibility is one of the important factors to achieve periodic guest accommodation in the nanospace enabling direct observation of gas molecules. Here, we report a convenient strategy to tune the framework flexibility by just an atomic exchange in a ligand, which enables us to easily construct a soft nanospace as the best platform to study gas adsorption. Indeed, we succeeded to observe C₂H₂ and CO₂ molecules confined in the pores of a flexible porous coordination polymer (PCP-N) in different configurations using SXRD measurement, whereas gas molecules in a rigid framework (PCP-C) isostructural to PCP-N were not seen crystallographically. The result of the coincident in situ powder X-ray diffraction and adsorption measurement for PCP-N unambiguously showed that the framework could flexibly transform to trap gas molecules with a commensurate fashion. In addition, for PCP-N, we found that the adsorbed gas molecules induced significant structural change involving dimensional change of the pore from one-dimensional to three-dimensional, and subsequently, additional gas molecules formed periodic molecular clusters in the nanospace.
Agid:
5416859