An ultra-dynamic anion-cluster-based organic framework
An ultra-dynamic anion-cluster-based organic framework
复制标题
DOI：
10.1016/j.chempr.2021.11.014
复制
发表时间：
2021-12
期刊：
影响因子：
23.5
通讯作者：
Jayanta Samanta;Rick W. Dorn;Wenlin Zhang;Xuanfeng Jiang;Mingshi Zhang;R. Staples;Aaron J. Rossini;Chenfeng Ke
中科院分区：
文献类型：
--
作者：
Jayanta Samanta;Rick W. Dorn;Wenlin Zhang;Xuanfeng Jiang;Mingshi Zhang;R. Staples;Aaron J. Rossini;Chenfeng Ke
能够动态扩展其空隙以吸引客户的多孔性有机框架仍然难以设计。挑战来自于在僵化和灵活性之间找到平衡。需要刚性才能保持框架，需要灵活性才能进行可逆的伸缩。在这里，我们引入了硫酸氢阴离子团簇作为软连接，构建了单晶氢键交联有机骨架HCOF-6。在摄取客体分子后，HCOF-6的阴离子团簇被破坏，使晶体迅速膨胀(<；40分钟)，达到其原始长度的两倍以上。除去这些客体后，HCOF-6的阴离子团簇和结晶度迅速恢复(<；10分钟)。这些客体诱导的材料尺寸膨胀和收缩是高度可逆的，分子动力学模拟和固体核磁共振实验证实了这种动态的阴离子团簇解离-再解离。HCOF-6的客体诱导尺寸变化突出了通过引入阴离子团簇来合成动态骨架材料的新途径。
Porous organic frameworks that can dynamically expand their voids to guest uptake remain formidable to design. The challenge comes from finding the balance between rigidity and flexibility. Rigidity is required to retain the framework, and the flexibility is needed for reversible expansion/contraction. Herein, we introduced bisulfate anion clusters as soft joints to construct a single-crystalline hydrogen-bonded cross-linked organic framework HCOF-6. Upon the uptake of guest molecules, the anion clusters of HCOF-6 were disrupted, allowing the crystal to expand rapidly (<40 min) to more than twice its original length. Removing these guests restored the anion clusters and the crystallinity of HCOF-6 quickly (<10 min). These guest-induced material size expansions and contractions are highly reversible, and the dynamic anion cluster dissociation-reassociation is confirmed by molecular dynamics simulations and solid-state NMR experiments. The guest-induced size change of HCOF-6 highlights a new approach to synthesize dynamic framework materials by introducing anion clusters.