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Guest-controlled incommensurate modulation in a meta-rigid metal–organic framework material

DOI: 10.1021/jacs.0c08794 DOI Help

Authors: Jiangnan Li (University of Manchester) , Zhengyang Zhou (Peking University) , Xue Han (University of Manchester) , Xinran Zhang (University of Manchester) , Yong Yan (University of Manchester) , Weiyao Li (University of Manchester) , Gemma L. Smith (University of Manchester) , Yongqiang Cheng (Oak Ridge National Laboratory) , Laura J. Mcormick Mpherson (Advanced Light Source) , Simon J. Teat (Advanced Light Source) , Mark D. Frogley (Diamond Light Source) , Svemir Rudic (ISIS Facility) , Anibal J. Ramirez-cuesta (Oak Ridge National Laboratory) , Alexander J. Blake (University of Nottingham) , Junliang Sun (Peking University) , Martin Schroeder (University of Manchester) , Sihai Yang (University of Manchester)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society

State: Published (Approved)
Published: October 2020
Diamond Proposal Number(s): 22137

Abstract: Structural transitions of host systems in response to guest binding dominate many chemical processes. We report an unprecedented type of structural flexibility within a meta-rigid material, MFM-520, which exhibits a reversible periodic-to-aperiodic structural transition resulting from a drastic distortion of a [ZnO4N] node controlled by the specific host–guest interactions. The aperiodic crystal structure of MFM-520 has no three-dimensional (3D) lattice periodicity but shows translational symmetry in higher-dimensional (3 + 2)D space. We have directly visualized the aperiodic state which is induced by incommensurate modulation of the periodic framework of MFM-520·H2O upon dehydration to give MFM-520. Filling MFM-520 with CO2 and SO2 reveals that, while CO2 has a minimal structural influence, SO2 can further modulate the structure incommensurately. MFM-520 shows exceptional selectivity for SO2 under flue-gas desulfurization conditions, and the facile release of captured SO2 from MFM-520 enabled the conversion to valuable sulfonamide products. MFM-520 can thus be used as a highly efficient capture and delivery system for SO2.

Journal Keywords: Adsorption; Crystal structure; Molecules; Metal organic frameworks; Physical and chemical processes

Subject Areas: Materials, Chemistry

Instruments: B22-Multimode InfraRed imaging And Microspectroscopy

Other Facilities: TOSCA at ISIS