Yang Shuliang, Akpinar Isil, Syzgantseva Olga A, Syzgantseva Maria A, Li Xuesong, Wu Guangcheng, Azad Chandra S, Han Han, Wang Xiaoliang, Xue Tianwei, Peng Li, Wu Yong, Zhang Ruihua, Zhang Long, Kwon Tae-Woo, Feng Liang, Jiao Yang, Stoddart J Fraser
Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.
College of Energy, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China.
J Am Chem Soc. 2025 Jun 25;147(25):21844-21854. doi: 10.1021/jacs.5c04895. Epub 2025 Jun 12.
As an emerging class of porous supports, metal-organic frameworks (MOFs) can host multifarious guests to realize diverse applications. Among the guest-introducing approaches, the in situ encapsulation method is unique in its ability to incorporate a diverse range of guests, from small organic molecules and metal clusters to proteins and even more complicated guests. Previous investigations have focused on guests that are either neutral or negatively charged. The realization of the in situ encapsulation of cationic catenanes in MOFs under mild conditions, however, has rarely been investigated. Herein, we have accomplished in situ encapsulation of a cationic catenane (DA[2]C) within UiO-66-F─a MOF consisting of Zr nodes and tetrafluoroterephthalic acid ligands─at room temperature using HO as a green solvent. Theoretical calculations elaborated that tetrafluoroterephthalic acid ligands interact strongly with the cationic DA[2]C. This observation is a result of electrostatic interactions between carboxylate anions and DA[2]C cations as well as the attraction of electronegative F atoms in tetrafluoroterephthalic acid to the cations. As a proof-of-concept application, the DA[2]C·4Cl/UiO-66-F composite demonstrated heterogeneous catalytic detoxification of 2-chloroethyl ethyl sulfide to the sulfoxide with a complete conversion rate (>99%) and high selectivity (>97%). This method could also be extended to other organic cationic molecules, including dibenzyl benzoimidazoloimidazole chloride and a pyrene-functionalized cyclobis(paraquat--phenylene), rendering it as a universal platform for constructing host-guest MOF systems with various applications.
作为一类新兴的多孔载体，金属有机框架材料（MOFs）可以容纳多种客体分子以实现多样化的应用。在引入客体分子的方法中，原位封装法具有独特之处，它能够纳入从小有机分子、金属簇到蛋白质甚至更复杂客体分子等各种各样的客体。以往的研究主要集中在中性或带负电荷的客体分子上。然而，在温和条件下实现阳离子索烃在MOFs中的原位封装却鲜有研究。在此，我们使用HO作为绿色溶剂，在室温下实现了阳离子索烃（DA[2]C）在UiO-66-F（一种由Zr节点和四氟对苯二甲酸配体组成的MOF）中的原位封装。理论计算表明，四氟对苯二甲酸配体与阳离子DA[2]C有强烈的相互作用。这一现象是由于羧酸根阴离子与DA[2]C阳离子之间的静电相互作用以及四氟对苯二甲酸中电负性F原子对阳离子的吸引所致。作为概念验证应用，DA[2]C·4Cl/UiO-66-F复合材料对2-氯乙基乙硫醚催化脱毒生成亚砜表现出多相催化活性，转化率达到100%（>99%），选择性高达97%以上。该方法还可以扩展到其他有机阳离子分子，包括二苄基苯并咪唑并咪唑氯化物和芘功能化的环双（百草枯-对亚苯基），使其成为构建具有各种应用的主客体MOF系统的通用平台。
