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

Guest-Controlled Incommensurate Modulation in a Meta-Rigid Metal-Organic Framework Material.
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超刚性金属有机物中客体控制的不相称调制

DOI:
10.1021/jacs.0c08794
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发表时间:
2020-11-11
影响因子:
15
通讯作者:
Yang S
Yang S
中科院分区:
化学1区
文献类型:
--
作者:
Li J;Zhou Z;Han X;Zhang X;Yan Y;Li W;Smith GL;Cheng Y;McCormick McPherson LJ;Teat SJ;Frogley MD;Rudić S;Ramirez-Cuesta AJ;Blake AJ;Sun J;Schröder M;Yang S

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由于客体结合,宿主系统的结构转变主导了许多化学过程。我们报道了一种在亚刚性材料MFM-520中前所未有的结构柔性,它表现出可逆的周期性到非周期性的结构转变,这是由特定的主-客体相互作用控制的[ZnO4N]节点的剧烈扭曲造成的。MFM-520的非周期晶体结构不具有三维(3D)晶格周期性,但在高维(3+2)维空间中具有平移对称性。我们直接可视化了MFM-520·H2O在脱水时由于周期骨架的无公度调制而引起的非周期态,从而得到了MFM-520。用二氧化碳和二氧化硫填充MFM-520表明,虽然二氧化碳对结构的影响最小,但二氧化硫可以进一步不相称地调节结构。MFM-520在烟气脱硫条件下对SO2表现出极高的选择性,从MFM-520捕获的SO2容易释放,使其能够转化为有价值的磺胺产品。因此,MFM-520可用作SO2的高效捕获和输送系统。
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.
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