Yang Ya-Ni, Wan Qiu-Yang, Zhu Meng-Jie, Ru Hua-Yang, Yang Ji-Kun, Li Qi, Zhou Meng, Chen Gaosong, Wu Yuchen, Jiang Lei, Zang Shuang-Quan
Henan Key Laboratory of Crystalline Molecular Functional Materials, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China.
Ministry of Education Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China.
J Am Chem Soc. 2025 Jul 30;147(30):26991-26999. doi: 10.1021/jacs.5c09304. Epub 2025 Jul 18.
Achieving efficient near-infrared (NIR) luminescence in atomically precise gold nanoclusters is challenging due to the strong vibrational freedom of the gold core. Herein, we synthesized two gold nanoclusters, [Au(PPh)Cl]Cl () and Au(PPh)Cl (), with comparable initial NIR photoluminescence quantum yields (PLQY, 0.3% and 0.32%, respectively), and systematically investigated their NIR piezoluminescence behaviors based on the hydrostatic pressure effect. Under high pressure, exhibits a significant NIR piezoluminescence enhancement. When the pressure increases to 3.6 GPa, the NIR-PLQY of amplifies from the initial 0.3% to 75.6%, which is the highest PLQY reported for solid-state gold nanoclusters. However, exhibits only monotonic pressure-induced luminescence quenching under compression. In situ high-pressure angle-dispersive X-ray diffraction experiments and theoretical calculations confirm the existence of distinct anisotropic compressions in and , which induce differential structural distortion of the gold core. The faster shrinkage along the -axis exacerbates the structural distortion of the core, whereas the more rapid compression along the -axis in suppresses the structural distortion of the gold core. High-pressure femtosecond transient absorption and Raman spectra synergistically demonstrate that pressure-driven directional structural distortion significantly suppresses nonradiative losses caused by low-frequency vibrations of the core along the -axis, resulting in NIR piezoluminescence enhancement of . Our study deeply reveals the intrinsic correlation between NIR-PLQY and metal core vibration relaxation at the atomic scale and provides a new approach to design and develop high-performance NIR luminescent materials.
由于金核具有很强的振动自由度，在原子精确的金纳米团簇中实现高效近红外（NIR）发光具有挑战性。在此，我们合成了两个金纳米团簇，[Au(PPh)Cl]Cl（）和Au(PPh)Cl（），它们具有可比的初始近红外光致发光量子产率（PLQY，分别为0.3%和0.32%），并基于静水压力效应系统地研究了它们的近红外压电发光行为。在高压下，表现出显著的近红外压电发光增强。当压力增加到3.6 GPa时，的近红外PLQY从初始的0.3%放大到75.6%，这是固态金纳米团簇报道的最高PLQY。然而，在压缩下仅表现出单调的压力诱导发光猝灭。原位高压角散射X射线衍射实验和理论计算证实了和中存在明显的各向异性压缩，这导致金核的不同结构畸变。沿轴更快的收缩加剧了核的结构畸变，而中沿轴更快的压缩抑制了金核的结构畸变。高压飞秒瞬态吸收和拉曼光谱协同表明，压力驱动的定向结构畸变显著抑制了核沿轴低频振动引起的非辐射损失，从而导致的近红外压电发光增强。我们的研究深入揭示了近红外PLQY与原子尺度上金属核振动弛豫之间的内在关联，并为设计和开发高性能近红外发光材料提供了一种新方法。
