Liu Haifei, Guo Chenxing, Li Luqi, Zhang Zeyuan, Hou Yali, Mu Chaoqun, Hou Gao-Lei, Zhang Zhenyi, Wang Heng, Li Xiaopeng, Zhang Mingming
State Key Laboratory for Mechanical Behavior of Materials, Shaanxi International Research Center for Soft Matter, School of Materials Science and Engineering, Xi'an Jiaotong University, Xi'an 710049, P. R. China.
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518055, P. R. China.
J Am Chem Soc. 2024 Jun 12;146(23):15787-15795. doi: 10.1021/jacs.4c01873. Epub 2024 May 13.
The encapsulation of different guest molecules by their different recognition domains of proteins leads to selective binding, catalysis, and transportation. Synthetic hosts capable of selectively binding different guests in their different cavities to mimic the function of proteins are highly desirable but challenging. Here, we report three ladder-shaped, triple-cavity metallacages prepared by multicomponent coordination-driven self-assembly. Interestingly, the porphyrin-based metallacage is capable of heteroleptic encapsulation of fullerenes (C or C) and coronene using its different cavities, allowing distinct allosteric recognition of coronene upon the addition of C or C. Owing to the different binding affinities of the cavities, the metallacage hosts one C molecule in the central cavity and two coronene units in the side cavities, while encapsulating two C molecules in the side cavities and one coronene molecule in the central cavity. The rational design of multicavity assemblies that enable heteroleptic encapsulation and allosteric recognition will guide the further design of advanced supramolecular constructs with tunable recognition properties.
蛋白质的不同识别域对不同客体分子的包封导致了选择性结合、催化和运输。能够在其不同空腔中选择性结合不同客体以模拟蛋白质功能的合成主体是非常理想的，但具有挑战性。在此，我们报道了通过多组分配位驱动自组装制备的三种梯形三空腔金属笼。有趣的是，基于卟啉的金属笼能够利用其不同的空腔对富勒烯（C或C）和蒄进行杂配体包封，在加入C或C时允许对蒄进行独特的变构识别。由于空腔的结合亲和力不同，金属笼在中央空腔中容纳一个C分子，在侧空腔中容纳两个蒄单元，而在侧空腔中包封两个C分子，在中央空腔中包封一个蒄分子。能够进行杂配体包封和变构识别的多空腔组装体的合理设计将指导具有可调识别特性的先进超分子构建体的进一步设计。
