Photoluminescence and Electrochemical Sensing of Atomically Precise Cu13 Cluster

doi:10.6023/A21050212

Abstract

Copper-based nanomaterials show widespread applications in the fields of luminescence and (bio)chemical sensing. Copper nanoclusters as a new class of nanomaterials have attracted extensive attention due to their atomic-level structure, but the syntheses of stable atom-precise copper clusters with good properties are still challenging. In this work, we have successfully prepared a novel mercaptoimidazole-stabilized copper(I) nanocluster: [Cu₁₃(SR)₁₂] NO₃ (Cu₁₃ NC, where RSH=2-mercaptobenzimidazole) by introducing the reducing agent (NaBH₄) in an acetonitrile-methanol solution of copper nitrate and RSH. The presence of NaBH₄ not only reduced Cu(II) to Cu(I) but also provided a reducing system to avoid the reversed oxidation. The structure and composition of Cu₁₃ NC have been collectively elucidated by X-ray crystallography and electrospray ionization mass spectrometry (ESI-MS). The metal framework of Cu₁₃ NC can be seen as three triangular bipyramids sharing one or two vertices, which are surrounded by 12 thiolate ligands as protecting agents through a simple bridging mode. Since the counterions in the crystal lattice are highly disordered and could not be located, the existence of NO₃^- has been confirmed by infrared spectroscopy and ESI-MS. Cu₁₃ NC exhibits good stability under ambient conditions and shows bright-red emission in the solid state (λ_em=627 nm). The long-life emission in the order of microseconds and large Stokes shift (≈280 nm) indicate that the luminescence of Cu₁₃ NC is a spin-forbidden triplet phosphorescence. The absolute quantum yield of the solid-state Cu₁₃ NC was calculated to be 1.36%. Meanwhile, there are two exposed copper atoms at each end of the structure, endowing Cu₁₃ with good electrochemical activity. The test confirmed that Cu₁₃ NC shows prompt response, and great selectivity in electrochemical detection of H₂O₂, making it a low-cost advanced H₂O₂ sensing material. This work provides an opportunity to investigate the structure-optical and electrochemical property relationship of copper clusters.

Key words: copper-thiolate cluster, atom-precise structure, photoluminescence, electrochemical sensing

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Hao-Nan Qin, Zhao-Yang Wang, Shuang-Quan Zang. Photoluminescence and Electrochemical Sensing of Atomically Precise Cu₁₃ Cluster[J]. Acta Chimica Sinica, 2021, 79(8): 1037-1041.

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Fig. & Tab. 4

Figure 1. (a) Total structure of Cu13 NC; (b) Cu13S12 frame; (c) Cu13 core formed by three vertex-sharing triangular biconicals. Color codes: Cu, brown and orange; S, yellow; C, gray; N, blue. H atoms are omitted for clarity

Figure 2. ESI mass spectrum of Cu13 NC in positive mode. Inset: comparison of the calculated (red) and experimental (black) isotope distribution patterns

Figure 3. (a) The photo of solid Cu13 NC under natural light and UV light respectively; (b) excitation and emission spectra of Cu13 NC in solid state at 298 K; (c) PL decays of a solid state of Cu13 NC at 298 K; (d) solid-state UV-vis absorption spectrum of Cu13 NC

Figure 4. (a) CVs of the Cu13 NC clusters in 0.1 mol•L-1 PBS; (b) the amperometric i-t curve of the Cu13 NC upon successive addition of H2O2 recorded at –0.56 V; (c) the linear relationship between responding current and concentration of H2O2; (d) the amperometric responses recorded on alternate addition of interfering chemicals and H2O2 in 0.1 mol•L-1 PBS; the concentration is 1×10-3 mol•L-1

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原子级结构精确Cu₁₃团簇的光致发光和电化学传感研究

Photoluminescence and Electrochemical Sensing of Atomically Precise Cu₁₃ Cluster

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原子级结构精确Cu13团簇的光致发光和电化学传感研究