학술논문
Triple Isomerism in 3D Covalent Organic Frameworks.
Document Type
Academic Journal
Author
Wang X; Laboratory for Zero-Carbon Energy, Institute of Innovative Research, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8550, Japan.; Department of Mechanical Engineering, School of Engineering, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8552, Japan.; Wada Y; Department of Chemistry, School of Science, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551, Japan.; Shimada T; Department of Chemistry, School of Science, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551, Japan.; Kosaka A; Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, Midori-ku, Yokohama 226-8503, Japan.; Adachi K; RIKEN Center for Emergent Matter Science (CEMS), Wako, Saitama 351-0198, Japan.; Hashizume D; RIKEN Center for Emergent Matter Science (CEMS), Wako, Saitama 351-0198, Japan.; Yazawa K; JEOL Ltd., Akishima, Tokyo 196-8558, Japan.; Uekusa H; Department of Chemistry, School of Science, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551, Japan.; Shoji Y; Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, Midori-ku, Yokohama 226-8503, Japan.; Fukushima T; Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, Midori-ku, Yokohama 226-8503, Japan.; Kawano M; Department of Chemistry, School of Science, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551, Japan.; Murakami Y; Laboratory for Zero-Carbon Energy, Institute of Innovative Research, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8550, Japan.; Department of Mechanical Engineering, School of Engineering, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8552, Japan.
Source
Publisher: American Chemical Society Country of Publication: United States NLM ID: 7503056 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-5126 (Electronic) Linking ISSN: 00027863 NLM ISO Abbreviation: J Am Chem Soc Subsets: PubMed not MEDLINE; MEDLINE
Subject
Language
English
Abstract
Isomerism in covalent organic frameworks (COFs) has scarcely been known. Here, for the first time we show 3D COFs with three framework isomers or polymorphs constructed from the same building blocks. All isomers were obtained as large (>10 μm) crystals; although their crystal shapes were distinctly different, they showed identical FT-IR and solid-state NMR spectra. Our structural analyses revealed unprecedented triple isomerism in 3D COFs (noninterpenetrated dia , qtz , and 3-fold interpenetrated dia-c3 nets). Furthermore, this Communication reports the first known COF with qtz topology for which the structure determination was based on Rietveld analysis. We achieved triple framework isomerism by reticulating a tetrahedral building block with a flexible junction and a linear building block with PEO side chains and by varying solution compositions. Our energy calculations, along with the discovery of interisomer transition, revealed that the isomer with qtz topology was a kinetic isomer. Thus, this simple yet little-explored concept of reticulating only flexible building blocks is an effective pathway to significantly broaden the diversity of 3D COFs, which have been proposed for a myriad of applications.