德国多特蒙德工业大学Clever, Guido H.团队报道了多组分[Pd₂ABCD]笼的非统计装配。相关研究成果于2024年1月19日发表在《自然—化学》。

受生物受体和催化剂的启发，自组装宿主在可持续合成、能量转换和医学方面显示出应用潜力。然而，在不冒自恋的自我排序或统计混乱的风险的情况下，以可区分的构建块的形式实现多种功能是很困难的。

该文中，研究人员报道了一系列完整的自组装异感笼，其中两个方形平面Pd^II阳离子通过协同效应被四个不同的双吡啶配体A、B、C和D桥接，专门形成单一的异构体——灯笼形笼[Pd₂ABCD]。这种自分选目标——仅形成55种可能结构中的一种——是在完全热力学控制下实现的，并且可以直接从配体和Pd^II阳离子或通过混合所有四个相应的同源性笼来逐步实现（通过组合前体，如[Pd₂A₂C₂]和[Pd₂B₂D₂D₂]）。合理设计复杂的多组分组件，实现不同化学部分的模块化结合，将提高其在功能纳米系统中的适用性。

附：英文原文

Title: Non-statistical assembly of multicomponent [Pd2ABCD] cages

Author: Wu, Kai, Benchimol, Elie, Baksi, Ananya, Clever, Guido H.

Issue&Volume: 2024-01-19

Abstract: Self-assembled hosts, inspired by biological receptors and catalysts, show application potential in sustainable synthesis, energy conversion and medicine. Implementing multiple functionalities in the form of distinguishable building blocks, however, is difficult without risking narcissistic self-sorting or a statistical mess. Here we report a systematic series of integratively self-assembled heteroleptic cages in which two square-planar PdII cations are bridged by four different bis-pyridyl ligands, A, B, C and D, via synergistic effects to exclusively form a single isomer—the lantern-shaped cage [Pd2ABCD]. This self-sorting goal—forming just one out of 55 possible structures—is reached under full thermodynamic control and can be realized progressively (by combining progenitors, such as [Pd2A2C2] with [Pd2B2D2]), directly from ligands and PdII cations or by mixing all four corresponding homoleptic cages. The rational design of complex multicomponent assemblies that enables the modular incorporation of diverse chemical moieties will advance their applicability in functional nanosystems.

DOI: 10.1038/s41557-023-01415-7

Source: https://www.nature.com/articles/s41557-023-01415-7