An Atomically Precise Pyrazolate-Protected Copper Nanocluster Exhibiting Exceptional Stability and Catalytic Activity

Angew Chem Int Ed Engl. 2023 Feb 20;62(9):e202218369. doi: 10.1002/anie.202218369. Epub 2023 Jan 18.

Abstract

The synthesis of atomically precise copper nanoclusters (Cu-NCs) with high chemical stability is a prerequisite for practical applications, yet still remains a long-standing challenge. Herein, we have prepared a pyrazolate-protected Cu-NC (Cu8), which exhibited exceptional chemical stability either in solid-state or in solution. The crystals of Cu8 are still suitable for single crystal X-ray diffraction analysis even after being treated with boiling water, 8 wt % H2 O2 , high concentrated acid (1 M HCl) or saturated base (≈20 M KOH), respectively. More importantly, the structure of Cu8 in solution also remained intact toward oxygen, organic acid (100 eq. HOAc) or base (400 eq. dibutylamine) confirmed by 1 H NMR and UV/Vis analysis. Taking advantage of high alkali-resistant, Cu8 illustrates excellent catalytic activity for the synthesis of indolizines, and it can be reused for at least 10 cycles without losing catalytic performance.

Keywords: Catalysis; Copper Nanocluster; Indolizines; Ligand Transformation; Pyrazolate.