Ma Xiangyu, Zhang Qiong, Li Jiale, Zhang Lidi, Li Guang, Zhang Zhongjie, Yu Haizhu, Zhu Manzhou
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials (Anhui University), Ministry of Education, Hefei, Anhui 230601, P. R. China.
School of Materials Science and Engineering, Anhui University, Institute of Physical Science and Information Technology, Anhui Key Laboratory of Information Materials and Devices, Hefei, Anhui 230601, P. R. China.
Inorg Chem. 2024 May 13;63(19):8775-8781. doi: 10.1021/acs.inorgchem.4c00465. Epub 2024 May 2.
The atomic precision of the subnanometer nanoclusters has provided sound proof on the structural correlation of metal complexes and larger-sized metal nanoparticles. Herein, we report the synthesis, crystallography, structural characterization, electrochemistry, and optical properties of a 133-atom intermetallic nanocluster protected by 57 thiolates (3-methylbenzenethiol, abbreviated as -MBTH) and 3 chlorides, with the formula of AgCu(-MBT)Cl. This is the largest Ag-Cu bimetallic cluster ever reported. Crystallographic analysis revealed that the nanocluster has a three-layer concentric core-shell structure, Ag@Ag@AgCuSCl, and the Ag metal kernel adopts a symmetry. The nuclei number is between that of the previously reported large silver cluster [Ag(SR)ClAg] and the large silver-rich cluster AuAg(SR) ( = 98). All these three clusters bear a similar metallic core structure, while the main structural difference lies in the shell motif structures. Electron counting revealed an open electron shell with 73 delocalized electrons, which was verified by the electron paramagnetic resonance analysis. The DPV electrochemical measurement indicates a multielectron state quantization double-layer charging shape and single-electron sequential charging and discharging characteristic of the AgCu alloy cluster. In addition, the open-hole Z-scan test reveals the nonlinear optical absorption (2-3 optical absorption in the NIR-II/III region) of AgCu nanoclusters.
亚纳米纳米团簇的原子精度为金属配合物与较大尺寸金属纳米颗粒之间的结构相关性提供了有力证据。在此，我们报道了一种由57个硫醇盐（3-甲基苯硫醇，缩写为-MBTH）和3个氯化物保护的133原子金属间纳米团簇的合成、晶体学、结构表征、电化学和光学性质，其化学式为AgCu(-MBT)Cl。这是迄今为止报道的最大的Ag-Cu双金属团簇。晶体学分析表明，该纳米团簇具有三层同心核壳结构，即Ag@Ag@AgCuSCl，且Ag金属核呈 对称。其核数介于先前报道的大银团簇[Ag(SR)ClAg]和富银大团簇AuAg(SR)（ = 98）之间。这三个团簇都具有相似的金属核结构，而主要的结构差异在于壳层基序结构。电子计数显示有一个具有73个离域电子的开放电子壳层，这一点通过电子顺磁共振分析得到了验证。差分脉冲伏安法（DPV）电化学测量表明，AgCu合金团簇具有多电子态量子化双层充电形状以及单电子顺序充放电特性。此外，开孔Z扫描测试揭示了AgCu纳米团簇的非线性光学吸收（在近红外II/III区域有2-3次光学吸收）。
