Guest-Controlled Incommensurate Modulation in a Meta-Rigid Metal–Organic Framework Material

Li, Jiangnan; Zhou, Zhengyang; Han, Xue; Zhang, Xinran; Yan, Yong; Li, Weiyao; Smith, Gemma L.; Cheng, Yongqiang; MCormick MPherson, Laura J.; Teat, Simon J.; Frogley, Mark D.; Rudić, Svemir; Ramirez-Cuesta, Anibal J.; Blake, Alexander J.; Sun, Junliang; Schröder, Martin; Yang, Sihai

doi:10.1021/jacs.0c08794

DOE OSTI · 1787222

Guest-Controlled Incommensurate Modulation in a Meta-Rigid Metal–Organic Framework Material

Li, Jiangnan·Zhou, Zhengyang·Han, Xue·Zhang, Xinran·Yan, Yong·Li, Weiyao·Smith, Gemma L.·Cheng, Yongqiang·MCormick MPherson, Laura J.·Teat, Simon J.·Frogley, Mark D.·Rudić, Svemir·Ramirez-Cuesta, Anibal J.·Blake, Alexander J.·Sun, Junliang·Schröder, Martin·Yang, Sihai

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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 [ZnO 4 N] 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. In this work, we have directly visualized the aperiodic state which is induced by incommensurate modulation of the periodic framework of MFM-520·H 2 O upon dehydration to give MFM-520. Filling MFM-520 with CO 2 and SO 2 reveals that, while CO 2 has a minimal structural influence, SO 2 can further modulate the structure incommensurately. MFM-520 shows exceptional selectivity for SO 2 under flue-gas desulfurization conditions, and the facile release of captured SO 2 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 SO 2 .

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Adsorption Crystal structure Metal organic frameworks Molecules Physical and chemical processes

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Li, Jiangnan, Zhou, Zhengyang, Han, Xue, Zhang, Xinran, Yan, Yong, Li, Weiyao, Smith, Gemma L., Cheng, Yongqiang, MCormick MPherson, Laura J., Teat, Simon J., Frogley, Mark D., Rudić, Svemir, Ramirez-Cuesta, Anibal J., Blake, Alexander J., Sun, Junliang, Schröder, Martin, Yang, Sihai. 2020-10-30. Guest-Controlled Incommensurate Modulation in a Meta-Rigid Metal–Organic Framework Material. https://doi.org/10.1021/jacs.0c08794

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