原子级结构精确Cu13团簇的光致发光和电化学传感研究

doi:10.6023/A21050212

摘要/Abstract

铜基纳米材料在发光和(生物)化学传感领域展现出广阔的应用前景. 铜纳米团簇作为一种新型的纳米材料, 由于其具有原子级精确的结构而引起了研究人员的广泛关注, 但是合成稳定并且具有优异性能的铜簇仍然具有挑战性. 本工作通过引入还原剂(NaBH₄)成功地制备出一种新型的巯基咪唑配体保护的一价铜纳米团簇[Cu₁₃(SR)₁₂]NO₃ (Cu₁₃ NC, 其中RSH=2-巯基苯并咪唑), 并通过单晶X射线衍射分析和电喷雾电离质谱(ESI-MS)对其结构和组成进行了表征. Cu₁₃ NC的金属骨架可以看成是三个三角双锥共享一个或两个顶点构成, 并通过简单的桥联模式被12个巯基配体保护. 固态Cu₁₃ NC具有良好的稳定性及亮红色的发光(λ_em=627 nm). 同时, 结构的两端有两个裸露的铜原子, 这使其在电化学检测H₂O₂的实验中表现出良好的电化学活性. 本工作为更好地研究纳米铜簇的结构和其光、电性能之间的联系提供了机会.

关键词: 铜硫簇, 原子级精确结构, 光致发光, 电化学传感

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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秦浩男, 王朝阳, 臧双全. 原子级结构精确Cu₁₃团簇的光致发光和电化学传感研究[J]. 化学学报, 2021, 79(8): 1037-1041.

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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图/表 4

图1. (a) Cu13 NC的整体结构; (b) Cu13S12框架; (c) 顶点共享的三角双锥体形成的Cu13核. 颜色代码: Cu 棕色和橙色; S 黄色; C 灰色; N 蓝色. 为了清楚起见, 省略了H原子

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

图2. 正模式下Cu13 NC的ESI质谱. 插图: 计算(红色)和实验(黑色)同位素分布图

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

图3. (a) 固体Cu13 NC在自然光和紫外光下的照片; (b) 298 K时固态Cu13 NC的激发和发射光谱; (c) 298 K时固态Cu13 NC的发射寿命谱图; (d) 固体Cu13 NC的紫外-可见吸收光谱

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

图4. (a) Cu13 NC在0.1 mol•L-1 PBS溶液中的CV曲线; (b) 在–0.56 V下连续加入H2O2时, Cu13 NC的i-t曲线; (c) 响应电流与H2O2浓度之间的线性关系; (d) 在0.1 mol•L-1 PBS中交替添加干扰化学物质和H2O2时的相应电流变化; 浓度均为1×10-3 mol•L-1

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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