Ligand-induced Assembly of Copper Nanoclusters with Enhanced Electrochemical Excitation and Radiative Transition for Electrochemiluminescence

Angew Chem Int Ed Engl. 2023 Oct 26;62(44):e202312053. doi: 10.1002/anie.202312053. Epub 2023 Sep 25.

Abstract

Copper nanoclusters (CuNCs) are emerging electrochemiluminescence (ECL) emitters with unique molecule-like electronic structures, high abundance, and low cost. However, the synthesis of CuNCs with high ECL efficiency and stability in a scalable manner remains challenging. Here, we report a facile gram-scale approach for preparing self-assembled CuNCs (CuNCsAssy ) induced by ligands with exceptionally boosted anodic ECL and stability. Compared to the disordered aggregates that are inactive in ECL, the CuNCsAssy shows a record anodic ECL efficiency for CuNCs (10 %, wavelength-corrected, relative to Ru(bpy)3 Cl2 /tripropylamine). Mechanism studies revealed the unusual dual functions of ligands in simultaneously facilitating electrochemical excitation and radiative transition. Moreover, the assembly addressed the limitation of poor stability of conventional CuNCs. As a proof of concept, an ECL biosensor for alkaline phosphatase detection was successfully constructed with an ultralow limit of detection of 8.1×10-6 U/L.

Keywords: Copper Nanoclusters; Electrochemical Excitation; Radiative Transition; Self-Assembly; Stability.

MeSH terms

  • Biosensing Techniques*
  • Copper* / chemistry
  • Electrochemical Techniques
  • Ligands
  • Luminescent Measurements

Substances

  • Copper
  • Ligands