Department of Chemistry, Texas A&M University , College Station, Texas 77843-3255, United States.
J Am Chem Soc. 2015 Sep 16;137(36):11801-9. doi: 10.1021/jacs.5b07373. Epub 2015 Sep 3.
A facile preparation of a mesoporous Cr-MOF, PCN-333(Cr) with functional group, has been demonstrated through a dual exchange strategy, involving a sequential ligand exchange and metal metathesis process. After optimization of the exchange system, the functionalized PCN-333(Cr), N3-PCN-333(Cr) shows well maintained crystallinity, porosity, as well as much improved chemical stability. Because of the exceptionally large pores (∼5.5 nm) in PCN-333(Cr), a secondary functional moiety, Zn-TEPP with a size of 18 Å × 18 Å, has been successfully clicked into the framework. In this article, we have also analyzed kinetics and thermodynamics during dual exchange process, showing our attempts to interpret the exchange event in the PCN-333. Our findings not only provide a highly stable mesoporous Cr-MOF platform for expanding MOF-based applications, but also suggest a route to functionalized Cr-MOF which may have not been achievable through conventional approaches.
一种通过双交换策略，包括顺序配体交换和金属复分解过程，简便地制备了具有官能团的介孔 Cr-MOF（PCN-333(Cr)）。在优化交换体系后，功能化的 PCN-333(Cr)，N3-PCN-333(Cr) 表现出良好的结晶度、孔隙率和显著提高的化学稳定性。由于 PCN-333(Cr) 具有特别大的孔（~5.5nm），可以成功地将尺寸为 18Å×18Å 的二级功能部分 Zn-TEPP 点击到骨架中。在本文中，我们还分析了双交换过程中的动力学和热力学，试图解释 PCN-333 中的交换事件。我们的发现不仅为扩展基于 MOF 的应用提供了一个高度稳定的介孔 Cr-MOF 平台，而且还为功能化的 Cr-MOF 提供了一种可能通过传统方法无法实现的途径。
