Dimensionality Transformation through Paddlewheel Reconfiguration in a Flexible and Porous Zn-Based Metal -- Organic Framework.
The reaction between Zn and a pyrene-based ligand decorated with benzoate fragments (HTBAPy) yields a 2D layered porous network with the metal coordination based on a paddlewheel motif. Upon desolvation the structure undergoes a significant and reversible structural adjustment with a corresponding r...
| Publicado en: | Journal of the American Chemical Society Vol. 134; no. 50; pp. 20466 - 20479 |
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| Autores principales: | , , , , , , , , , , , , , , |
| Formato: | Artículo |
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American Chemical Society
12/19/2012
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| 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=84582915&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 84582915 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: 12/19/2012 vid: 134 iid: 50 pid: 997 pub: American Chemical Society artinfo: ui: 84582915 10.1021/ja308995t ppf: 20466 ppct: 13 formats: tig: atl: Dimensionality Transformation through Paddlewheel Reconfiguration in a Flexible and Porous Zn-Based Metal -- Organic Framework. aug: au: Stylianou, Kyriakos C. Rabone, Jeremy Chong, Samantha Y. Heck, Romain Armstrong, Jayne Wiper, Paul V. Jelfs, Kim E. Zlatogorsky, Sergey Bacsa, John McLennan, Alec G. Ireland, Christopher P. Khimyak, Yaroslav Z. Thomas, K. Mark Bradshaw, Darren Rosseinsky, Matthew J. affil: Department of Chemistry University of Liverpool Liverpool L69 7ZD U.K. Northern Carbon Research Laboratories Sir Joseph Swan Institute and School of Chemical Engineering and Advanced Materials Bedson Building Newcastle University Newcastle upon Tyne NE1 7RU U.K. su: Metal-organic frameworks Zinc Pyrene Coordinate covalent bond Xylene Ligand binding (Biochemistry) Porous materials synthesis sug: subj: Metal-organic frameworks Zinc Pyrene Coordinate covalent bond Xylene Ligand binding (Biochemistry) Porous materials synthesis ab: The reaction between Zn and a pyrene-based ligand decorated with benzoate fragments (HTBAPy) yields a 2D layered porous network with the metal coordination based on a paddlewheel motif. Upon desolvation the structure undergoes a significant and reversible structural adjustment with a corresponding reduction in crystallinity. The combination of computationally assisted structure determination and experimental data analysis of the desolvated phase revealed a structural change in the metal coordination geometry from square-pyramidal to tetrahedral. Simulations of desolvation showed that the local distortion of the ligand geometry followed by the rotation and displacement of the pyrene core permits the breakup of the metal-paddlewheel motifs and the formation of 1D Zn -- O chains that cross-link adjacent layers resulting in a dimensionality change from the 2D layered structure to a 3D structure. Constrained Rietveld refinement of the powder X-ray diffraction pattern of the desolvated phase and the use of other analytical techniques such as porosity measurements 13C CP MAS NMR spectroscopy and fluorescence spectroscopy strongly supported the observed structural transformation. The 3D network is stable up to 425 °C and is permanently porous to CO with an apparent BET surface area of 523(8) m/g (p/p° = 0.02 -- 0.22). Because of the hydrophobic nature size and shape of the pores of the 3D framework the adsorption behavior of the structure toward p-xylene and m-xylene was studied and the results indicated that the shape of the isotherm and the kinetics of the adsorption process are determined mainly by the shape of the xylene isomers with each xylene isomer interacting with the host framework in a different manner. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2012 holdings: @attributes: islocal: N |
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