具有可定制光学限幅效应的不稳定配体保护的 Cu50 纳米团簇,ACS Materials Letters

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具有可定制光学限幅效应的不稳定配体保护的 Cu50 纳米团簇
ACS Materials Letters ( IF 9.6 ) Pub Date : 2023-12-19 , DOI: 10.1021/acsmaterialslett.3c01305
Jing Sun _{1,

2} , Xiongkai Tang ₃ , Zhuang-Hua Liu ₄ , Zhenlang Xie ₃ , Bingzheng Yan ₁ , Runfang Yin ₁ , Chaolumen Chaolumen ₂ , Jian Zhang ₄ , Weihui Fang ₄ , Jianyu Wei ₅ , Hui Shen ₁

Affiliation

原子精确的铜纳米团簇最近引起了极大的关注，因为它们通常表现出与金和银对应物不同的结构和特性。尽管在铜纳米团簇的制备和结构确定方面已经取得了相当大的进展，但将这些新创造的材料引入非线性光学等更基础的领域仍处于起步阶段。在此，我们报告了一类新的 Cu ₅₀纳米团簇，表现出可调谐的光学限幅效应。这项工作中报道的简便制备原型允许发现多达四个具有几乎相同金属骨架的簇，即 Cu ₅₀ (CF ₃ COO) ₁₂ (3,5- di Me-PhS) ₁₈ (PPh ₃ ) ₄ H ₂ (Cu ₅₀ -1)、Cu ₅₀ (CF ₃ COO) ₁₀ (4-F-PhS) ₂₀ (PPh ₃ ) ₆ H ₂ (Cu ₅₀ -2)、Cu ₅₀ (CF ₃ COO) ₁₀ (PhS) ₂₀ (PPh ₃ ) ₆ H ₂ (Cu ₅₀ -3)、Cu ₅₀ (PhCOO) ₁₀ (4-F-PhS) ₂₀ (PPh ₃ ) ₆ H ₂ (Cu ₅₀ -4)。X 射线单晶分析揭示了Cu ₅₀系列的分子结构，描述了硫醇盐-羧酸盐-膦-铜有机金属壳对Cu _{44核的稳定作用。}通过电喷雾电离质谱 (ESI-MS)、核磁共振 (NMR) 和密度泛函理论 (DFT) 计算的组合研究表明，这些团簇包含 18 个自由价电子，这使得它们可能是第一个具有 18e 的铜超原子库。纳秒 Z 扫描测量结果表明，团簇表现出典型的光学限幅效应，表明它们在非线性光学 (NLO) 领域的应用前景良好。_{更重要的是，Cu 50}上不稳定的表面图案使我们能够调整其 NLO 特性。这项工作不仅报道了一种新型原子级精确的铜纳米团簇，具有简便的制备过程、清晰的结构和不稳定的表面图案，而且还鼓励在更令人兴奋的领域探索铜纳米团簇的研究。

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Labile Ligands Protected Cu50 Nanoclusters with Tailorable Optical Limiting Effect

Atomically precise copper nanoclusters have recently attracted tremendous attention, as they often exhibit structures and properties distinct to their gold and silver counterparts. Although considerable progress has been made in the preparation and structure determination of copper nanoclusters, the introduction of those newly created materials in more underlying areas such as nonlinear optics is in its infancy. Herein, we report a new class of Cu₅₀ nanoclusters exhibiting a tunable optical limiting effect. The facile preparation prototype reported in this work allows the discovery of up to four clusters with the nearly identical metal framework, namely, Cu₅₀(CF₃COO)₁₂(3,5-diMe-PhS)₁₈(PPh₃)₄H₂ (Cu₅₀-1), Cu₅₀(CF₃COO)₁₀(4-F-PhS)₂₀(PPh₃)₆H₂ (Cu₅₀-2), Cu₅₀(CF₃COO)₁₀(PhS)₂₀(PPh₃)₆H₂ (Cu₅₀-3), and Cu₅₀(PhCOO)₁₀(4-F-PhS)₂₀(PPh₃)₆H₂ (Cu₅₀-4). The molecular structure of the Cu₅₀ series, as revealed by X-ray single crystal analysis, describes the stabilization of Cu₄₄ core by an organometallic shell of thiolate-carboxylate-phosphine-copper. The combinatorial studies by electrospray ionization mass spectroscopy (ESI-MS), nuclear magnetic resonance (NMR), and density functional theory (DFT) calculations suggest that the clusters contain 18 free valence electrons, making them probably the first library of copper superatoms featuring 18e. As revealed by the nanosecond Z-scan measurements results, the clusters exhibit typical optical limiting effects, indicating their promising applications in the field of nonlinear optics (NLO). More importantly, the labile surface motifs on Cu₅₀ allow us to tune their NLO properties. This work not only reports a new class of atomically precise copper nanoclusters with facile preparation process, clear structures, and labile surface motifs but also encourages research on the exploration of copper nanoclusters in more exciting areas.

更新日期：2023-12-19

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