近日，北京理工大学孙建科团队研究了基于金属簇的开放框架内封装的有机笼：具有主体间电荷协作的主体材料中的单晶主体。相关论文于2025年4月28日发表在《德国应用化学》杂志上。

将离散有机笼和无机簇的不同构建单元整合到具有定制结构和协同功能的单晶超分子框架中是一项重大挑战。研究组介绍了通过静电驱动阳离子铵有机笼与阴离子碘化铅簇的自组装来实现这种杂化物的发现。值得注意的是，通过仔细调节阳离子有机笼的大小、形状和组成，他们在宿主结构中构建了一个完整的多孔宿主。在这个系统中，内部阳离子笼紧密地驻留在由阴离子碘化铅簇构成的外部网络中。这种独特的嵌套层次结构展示了静电力促进的增强的宿主间相互作用，静电力错综复杂地定制了碘化铅外部部分的电子结构。 

因此，正如综合实验和理论分析所证实的那样，这种杂化物表现出了独特的光物理特性，包括高效的氧活化和增强的光热转换能力。通过与包含碘化铅簇和中性胺笼的宿主结构中结构相似的宿主进行系统比较，进一步证明了宿主间静电相互作用的关键作用。此外，整合和分隔的双宿主充当级联反应的空间隔离的双活性位点，与缺乏电荷合作的结构对应物相比，活性提高了33~47倍。

附：英文原文

Title: Organic Cage Encapsulated within Metal Cluster-Based Open Frameworks: A Single-Crystal Host-in-Host Material with Inter-Host Charge Cooperation

Author: Zhao-Feng Wu, Jing-Wang Cui, Ke Zhao, Bin Tan, Si-Hua Liu, Xiao-Ying Huang, Jian-Ke Sun, Guo-Yu Yang

Issue&Volume: 2025-04-28

Abstract: Integrating dissimilar building units of discrete organic cages and inorganic clusters into single-crystal supramolecular frameworks with tailored architectures and synergistic functions presents a significant challenge. Here, we presented our discovery of achieving such hybrids through electrostatically driven self-assembly of cationic ammonium organic cages with anionic lead iodide clusters. Notably, by carefully modulating the size, shape and composition of cationic organic cages, we have constructed an integrated porous host-in-host architecture. In this system, the internal cationic cage snugly resided, encapsulated within the external network constructed from anionic lead iodide clusters. This unique nested hierarchy showcased enhanced interhost interactions facilitated by electrostatic forces, which intricately tailored the electronic structure of the outer lead iodide moiety. As a result, the hybrid demonstrated distinguished photophysical properties, including efficient oxygen activation and enhanced photothermal conversion capability, as confirmed by comprehensive experimental and theoretical analyses. The critical role of interhost electrostatic interactions was further demonstrated through a systematic comparison with a structurally similar host-in-host architecture comprising lead iodide clusters and neutral amine cages. Furthermore, the integrated and compartmentalized dual-host served as spatially isolated dual active sites for cascade reactions, exhibiting 33~47 folds enhancement in activity compared to structural counterparts lacking charge cooperation.

DOI: 10.1002/anie.202501803

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202501803