Cooperative Bond Scission in a Soft Porous Crystal Enables Discriminatory Gate Opening for Ethylene over Ethane.
Here we report a soft porous crystal possessing hemilabile cross-links in its framework that exhibits exclusive gate opening for ethylene, enabling the discriminatory adsorption of ethylene over ethane. A Co-based porous coordination polymer (PCP) bearing vinylogous tetrathiafulvalene (VTTF) ligands...
| Publicado en: | Journal of the American Chemical Society Vol. 139; no. 50; pp. 18313 - 18322 |
|---|---|
| Autores principales: | , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
12/20/2017
|
| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=127093255&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 127093255 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 12/20/2017 vid: 139 iid: 50 pid: 997 pub: American Chemical Society artinfo: ui: 127093255 10.1021/jacs.7b10110 ppf: 18313 ppct: 9 formats: tig: atl: Cooperative Bond Scission in a Soft Porous Crystal Enables Discriminatory Gate Opening for Ethylene over Ethane. aug: au: Sen, Susan Nobuhiko Hosono Jia-Jia Zheng Shinpei Kusaka Ryotaro Matsuda Shigeyoshi Sakaki Susumu Kitagawa affil: Institute for Integrated Cell-Material Sciences, Kyoto University Institute for Advanced Study, Kyoto University, Yoshida Ushinomiya-cho, Sakyo-ku, Kyoto 606-8501, Japan Fukui Institute for Fundamental Chemistry, Kyoto University, Takano Nishihiraki-cho 34-4, Sakyo-ku, Kyoto 606-8103, Japan Department of Chemistry and Biotechnology, School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan. su: Ethylene synthesis Scission (Chemistry) Adsorption capacity Intermolecular interactions Density functional theory sug: subj: Ethylene synthesis Scission (Chemistry) Adsorption capacity Intermolecular interactions Density functional theory ab: Here we report a soft porous crystal possessing hemilabile cross-links in its framework that exhibits exclusive gate opening for ethylene, enabling the discriminatory adsorption of ethylene over ethane. A Co-based porous coordination polymer (PCP) bearing vinylogous tetrathiafulvalene (VTTF) ligands, [Co(VTTF)], forms Co−S bonds as intermolecular cross-links in its framework in the evacuated closed state. The PCP recognizes ethylene via d−π complexation on the accessible metal site that displaces and cleaves the Co−S bond to “unlock†the closed structure. This ethylene-triggered unlocking event facilitates remarkable nonporous-to-porous transformations that open up accessible void space. This structural transformation follows a two-step gate-opening process. Each phase, including the intermediate structure, was successfully characterized by single-crystal X-ray diffraction analysis, which revealed an intriguing “half-open†structure suggestive of a disproportionate gate-opening phenomenon. The gate-opening mechanism was also investigated theoretically; density functional theory and Monte Carlo calculations revealed that the unique “half-open†phase corresponds to a substantially stable intermediate over the possible transformation trajectories. While ethylene opens the gate, ethane does not because it is unable to coordinate to the Co center. This feature is maintained even at pressures above 1 MPa and at a temperature of 303 K, demonstrating the potential of the “gate-locking/unlocking†mechanism that exploits the hemilabile cross-linking in soft porous crystals. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2017 holdings: @attributes: islocal: N |
|---|