Structural distortion and electron redistribution in dual-emitting gold nanoclusters
Structural distortion and electron redistribution in dual-emitting gold nanoclusters
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DOI：
10.1038/s41467-020-16686-8
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发表时间：
2020-06-09
影响因子：
16.6
通讯作者：
Jin, Rongchao
中科院分区：
文献类型：
--
作者：
Li, Qi;Zhou, Dongming;Jin, Rongchao
破译复杂的激发态过程对于开发不同用途的发射可控发光材料是至关重要的。在这里，我们报告了在一系列金纳米团簇中，伴随着电子重新分布的光致结构扭曲的出现。这种意想不到的缓慢激发态转变过程导致了具有延长发光寿命的近红外双发射。我们证明了这种双重发射对溶剂的极性、粘度、温度和压力表现出高度灵敏和比率的响应。因此，基于这一策略开发了一种多功能的多环境参数发光纳米传感器。此外，我们完全揭开了这种意想不到的激发态转变的原子级结构起源，并通过剪裁金纳米团簇的双四面体核心结构展示了对转变动力学的控制。总体而言，这项工作为发光纳米团簇的激发态物理化学提供了实质性的进展，并为下一代纳米探测器、传感器和开关的合理设计提供了一般策略。在分子中观察到的激发态结构和电子变化在纳米材料中受到阻碍。在这里，作者确定了三个光激发的金纳米团簇的结构扭曲和电子重新分布，连接了分子和纳米晶区，使四面体核心单元的灵活性成为可能。
Deciphering the complicated excited-state process is critical for the development of luminescent materials with controllable emissions in different applications. Here we report the emergence of a photo-induced structural distortion accompanied by an electron redistribution in a series of gold nanoclusters. Such unexpected slow process of excited-state transformation results in near-infrared dual emission with extended photoluminescent lifetime. We demonstrate that this dual emission exhibits highly sensitive and ratiometric response to solvent polarity, viscosity, temperature and pressure. Thus, a versatile luminescent nano-sensor for multiple environmental parameters is developed based on this strategy. Furthermore, we fully unravel the atomic-scale structural origin of this unexpected excited-state transformation, and demonstrate control over the transition dynamics by tailoring the bi-tetrahedral core structures of gold nanoclusters. Overall, this work provides a substantial advance in the excited-state physical chemistry of luminescent nanoclusters and a general strategy for the rational design of next-generation nano-probes, sensors and switches. Excited-state structural and electronic changes, observed in molecules, are hampered in nanomaterials. Here the authors identify structural distortion and electron redistribution in three photoexcited gold nanoclusters, connecting molecular and nanocrystal regimes, enabled by flexibility of the tetrahedral core units.