Regulation of lanthanide supramolecular nanoreactors via a bimetallic cluster cutting strategy to boost aza-Darzens reactions

Jingzhe Li, Manchang Kou, Shengbin Zhou, Fan Dong, Xiaoyu Huang, Xiaoliang Tang (), Yu Tang () and Weisheng Liu ()
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Jingzhe Li: Lanzhou University
Manchang Kou: Lanzhou University
Shengbin Zhou: Lanzhou University
Fan Dong: Lanzhou University
Xiaoyu Huang: Lanzhou University
Xiaoliang Tang: Lanzhou University
Yu Tang: Lanzhou University
Weisheng Liu: Lanzhou University

Nature Communications, 2025, vol. 16, issue 1, 1-13

Abstract: Abstract Supramolecular nanoreactor as artificial mimetic enzyme is attracting a growing interest due to fine-tuned cavity and host-guest molecular recognition. Here, we design three 3d-4f metallo-supramolecular nanocages with different cavity sizes and active sites (Zn2Er4L14, Zn4Er6L26, and Zn2Er8L38) based on a “bimetallic cluster cutting” strategy. Three nanocages exhibit a differential catalysis for the three-component aza-Darzens reaction without another additive, and only Zn2Er8L38 with the largest cavity and the most lanthanides centers has excellent catalytic conversion for monosubstituted and disubstituted N-aryl aziridine products. The host-guest relationship investigations confirm that Zn2Er8L38 significantly outperforms Zn2Er4L14 with the smaller cavity and Zn4Er6L26 with the fewer Lewis acidic sites in multi-component reaction is mainly attributed to the synergy of inherent confinement effect and multiple Lewis acidic sites in nanocage. The “bimetallic cluster cutting” strategy for the construction of 3d−4f nanocages with large windows may represent a potential approach to develop supramolecular nanoreactor with high catalytic efficiency.

Date: 2025
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DOI: 10.1038/s41467-024-54950-3

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