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

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 (Zn 2 Er 4 L 1 4 , Zn 4 Er 6 L 2 6 , and Zn 2 Er 8 L 3 8 ) 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 Zn 2 Er 8 L 3 8 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 Zn 2 Er 8 L 3 8 significantly outperforms Zn 2 Er 4 L 1 4 with the smaller cavity and Zn 4 Er 6 L 2 6 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.