Rational Design and Reticulation of Infinite qbe Rod Secondary Building Units into Metal–Organic Frameworks through a Global Desymmetrization Approach for Inverse C3H8/C3H6 Separation
Articolo
Data di Pubblicazione:
2024
Citazione:
Rational Design and Reticulation of Infinite qbe Rod Secondary Building Units into Metal–Organic Frameworks through a Global Desymmetrization Approach for Inverse C3H8/C3H6 Separation / W. Gong, Y. Xie, A. Yamano, S. Ito, E.W. Reinheimer, J. Dong, C.D. Malliakas, D.M. Proserpio, Y. Cui, O.K. Farha. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - 63:5(2024 Jan 25), pp. e202318475.1-e202318475.9. [10.1002/anie.202318475]
Abstract:
The development of reticular chemistry has enabled the construction of a large array of metal-organic frameworks (MOFs) with diverse net topologies and functions. However, dominating this class of materials are those built from discrete/finite secondary building units (SBUs), yet the designed synthesis of frameworks involving infinite rod-shaped SBUs remain underdeveloped. Here, by virtue of a global linker desymmetrization approach, we successfully targeted a novel Cu-MOF (Cu-ASY) incorporating infinite Cu-carboxylate rod SBUs with its structure determined by micro electron diffraction (MicroED) crystallography. Interestingly, the rod SBU can be simplified as a unique cylindric sphere packing qbe tubule made of [43 .62 ] tiles, which further connect the tritopic linkers to give a newly discovered 3,5-connected gfc net. Cu-ASY is a permanent ultramicroporous material featuring 1D channels with highly inert surfaces and shows a preferential adsorption of propane (C3 H8 ) over propene (C3 H6 ). The efficiency of C3 H8 selective Cu-ASY is validated by multicycle breakthrough experiments, giving C3 H6 productivity of 2.2 L/kg. Density functional theory (DFT) calculations reveal that C3 H8 molecules form multiple C-H⋅⋅⋅π and atypical C-H⋅⋅⋅ H-C van der Waals interactions with the inner nonpolar surfaces. This work therefore highlights the linker desymmetrization as an encouraging and intriguing strategy for achieving unique MOF structures and properties.
Tipologia IRIS:
01 - Articolo su periodico
Keywords:
Desymmetrization; Gas Separation; Metal-Organic Framework; Rod SBU; Topology;
Elenco autori:
W. Gong, Y. Xie, A. Yamano, S. Ito, E.W. Reinheimer, J. Dong, C.D. Malliakas, D.M. Proserpio, Y. Cui, O.K. Farha
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