Department of Chemistry , Texas A&M University , College Station , Texas 77843-3255 , United States.
Department of Materials Science and Engineering , Texas A&M University , College Station , Texas 77843-3003 , United States.
J Am Chem Soc. 2019 Sep 18;141(37):14524-14529. doi: 10.1021/jacs.9b06917. Epub 2019 Sep 6.
Sophisticated chemical processes widely observed in biological cells require precise apportionment regulation of building units, which inspires researchers to develop tailorable architectures with controllable heterogeneity for replication, recognition and information storage. However, it remains a substantial challenge to endow multivariate materials with internal sequences and controllable apportionments. Herein, we introduce a novel strategy to manipulate the apportionment of functional groups in multivariate metal-organic frameworks (MTV-MOFs) by preincorporating interlocked linkers into framework materials. As a proof of concept, the imprinted apportionment of functional groups within ZIF-8 was achieved by exchanging imine-based linker templates with original linkers initially. The removal of linker fragments by hydrolysis can be achieved via postsynthetic labilization, leading to the formation of architectures with controlled heterogeneity. The distributions of functional groups in the resulting imprinted MOFs can be tuned by judicious control of the interlocked chain length, which was further analyzed by computational methods. This work provides synthetic tools for precise control of pore environment and functionality sequences inside multicomponent materials.
复杂的化学过程在生物细胞中广泛存在，需要对构建单元进行精确的分配调控，这启发研究人员开发出具有可复制性、可识别性和信息存储能力的可控异质结构的可定制架构。然而，赋予多元材料内部序列和可控分配仍然是一个重大挑战。在此，我们引入了一种新策略，通过将互锁链接器预先纳入框架材料来操纵多元金属-有机骨架（MTV-MOF）中功能基团的分配。作为概念验证，通过最初用原始链接器交换基于亚胺的链接模板，在 ZIF-8 内实现了功能基团的印迹分配。通过后合成的不稳定化可以实现链接片段的水解去除，从而形成具有可控异质结构的架构。通过合理控制互锁链长，可以调节所得印迹 MOF 中功能基团的分布，这可以通过计算方法进一步分析。这项工作为精确控制多组分材料内部的孔环境和功能序列提供了合成工具。
