Pore Size Engineering of MOFs by Pore Edge Reaction: Tetrazine Click and Hydrogen Adsorption in Theory and Experiment.

IF 7 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Chemistry of Materials Pub Date : 2025-07-02 eCollection Date: 2025-07-22 DOI:10.1021/acs.chemmater.5c00914

Damian Jędrzejowski, Michał Ryndak, Gabriela Jajko-Liberka, Paweł Kozyra, Witold Piskorz, Volodymyr Bon, Stefan Kaskel, Dariusz Matoga

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Abstract

Precise control over the porosity of metal-organic frameworks (MOFs) is crucial to optimize their properties and leverage their inherent tunability. However, there are ongoing challenges in pore size engineering for each MOF platform such as preserving crystallinity and morphology and facilitating reliable theoretical predictions throughout a series of modulated structures. Among postsynthetic strategies, mainly covalent functionalization appears to simultaneously preserve structural integrity and enable accurate theoretical predictions. Here, we present a MOF platform [M₂(RCOO)₄(H₂O)₂], JUK-21-(M), M = Cu or Zn, containing a tetrazine-based tetracarboxylate linker, which we covalently functionalize using the inverse electron-demand Diels-Alder reaction (iEDDA) and five dienophiles of various bulkiness, yielding a series of JUK-21-(Cu)-x MOFs. In addition to experiments, the iEDDA reactivity is assessed by applying a charge distribution susceptibility analysis, including Fukui functions, hardness, and relevant donor/acceptor orbitals. Comprehensive theoretical and experimental insights into the adsorption of nitrogen and hydrogen by JUK-21-(Cu)-x enable rationalization of the observed isotherms and show the isosteric heat of hydrogen adsorption as a highly sensitive parameter to validate the modification efficiency. Our findings indicate to what extent the pore size of MOFs affects the adsorption properties and highlight potential pitfalls that arise even with the precise covalent functionalization of MOFs.

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基于孔边反应的mof孔径工程：理论与实验的四嗪吸附与氢吸附。

精确控制金属有机骨架（mof）的孔隙率对于优化其性能和利用其固有的可调性至关重要。然而，每个MOF平台的孔径工程都面临着挑战，例如在一系列调制结构中保持结晶度和形态，并促进可靠的理论预测。在合成后策略中，主要的共价功能化似乎同时保持了结构的完整性并能够进行准确的理论预测。在这里，我们提出了一个MOF平台[M2(RCOO)4(H2O)2], JUK-21-(M), M = Cu或Zn，含有四嗪基四羧酸酯连接剂，我们使用逆电按需diols - alder反应（iEDDA）和五种不同体积的亲二烯试剂进行共价功能化，得到了一系列JUK-21-(Cu)-x MOF。除实验外，还通过电荷分布敏感性分析（包括福井函数、硬度和相关的供体/受体轨道）来评估iEDDA的反应性。对JUK-21-(Cu)-x对氮和氢的吸附进行了全面的理论和实验研究，使观察到的等温线合理化，并表明氢吸附的等容热是一个高度敏感的参数，可以验证改性效率。我们的研究结果表明，mof的孔径大小在多大程度上影响了吸附性能，并突出了mof的潜在缺陷，即使是精确的共价功能化。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Chemistry of Materials 工程技术-材料科学：综合

CiteScore

14.10

自引率

5.80%

发文量

929

审稿时长

1.5 months

期刊介绍： The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.