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Dimensionality Transformation through Paddlewheel Reconfiguration in a Flexible and Porous Zn-Based Metal-Organic Framework

Lookup NU author(s): Emeritus Professor Mark ThomasORCiD


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The reaction between Zn and a pyrene-based ligand decorated with benzoate fragments (H(4)TBAPy) 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 ID 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, C-13 CP MAS NMR spectroscopy, and fluorescence spectroscopy strongly supported the observed structural transformation. The 3D network is stable up to 425 degrees C and is permanently porous to CO2 with an apparent BET surface area of 523(8) m(2)/g (p/p degrees = 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.

Publication metadata

Author(s): Stylianou KC, Rabone J, Chong SY, Heck R, Armstrong J, Wiper PV, Jelfs KE, Zlatogorsky S, Bacsa J, McLennan AG, Ireland CP, Khimyak YZ, Thomas KM, Bradshaw D, Rosseinsky MJ

Publication type: Article

Publication status: Published

Journal: Journal of the American Chemical Society

Year: 2012

Volume: 134

Issue: 50

Pages: 20466-20478

Print publication date: 05/11/2012

ISSN (print): 0002-7863

ISSN (electronic): 1520-5126

Publisher: American Chemical Society


DOI: 10.1021/ja308995t


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