Parity-forbidden superatomic molecular orbital interaction and aurophilicity induced H─Au bonding in H@Au20

IF 11.7 1区综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES

Science Advances Pub Date : 2025-07-25 DOI:10.1126/sciadv.adx2053

Chenxi Wan, Xinrui Yang, Zhen Gong, Rui Li, Yulei Shi, Boon K. Teo, Zhigang Wang

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Abstract

Understanding H─Au interaction is essential for elucidating the stereochemistry and reactivity of gold hydrides. By embedding a hydrogen atom in the central tetrahedral cavity of Au₂₀, we identify a distinct form of hydrogen-mediated bonding in a gold cluster. Our results show that the H─Au bonding can be described as a process wherein H─Au interactions compensate for relatively weaker Au─Au bonding driven by intrinsic aurophilic interactions. This phenomenon originates from parity-forbidden coupling of superatomic molecular orbitals under a noncentrosymmetric field, giving rise to the atypical H─Au bonding and a formally neutral interstitial H atom. A detailed analysis of optical properties reveals partial suppression of visible-light absorption and emergence of a more favorable phosphorescent channel, a manifestation of the complex nature of this H─Au bonding. These findings suggest a versatile platform for tuning electronic and optical properties of gold cluster systems through subtle atomic-level manipulation.

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偶对禁止的超原子分子轨道相互作用和亲水性诱导了H@Au20中的H─Au键

了解H - Au相互作用对于阐明金氢化物的立体化学和反应性至关重要。通过在Au20的中心四面体腔中嵌入一个氢原子，我们在金簇中发现了一种独特形式的氢介导键。我们的研究结果表明，H─Au键可以描述为H─Au相互作用补偿由内在亲金相互作用驱动的相对弱的Au─Au键的过程。这一现象源于非中心对称场下超原子分子轨道的奇偶禁止耦合，产生非典型的H─Au键和形式中性的间隙H原子。光学性质的详细分析揭示了部分抑制可见光吸收和出现更有利的磷光通道，这是这种H─Au键复杂性质的表现。这些发现为通过微妙的原子水平操纵来调整金团簇系统的电子和光学特性提供了一个通用的平台。

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来源期刊

Science Advances 综合性期刊-综合性期刊

CiteScore

21.40

自引率

1.50%

发文量

1937

审稿时长

29 weeks

期刊介绍： Science Advances, an open-access journal by AAAS, publishes impactful research in diverse scientific areas. It aims for fair, fast, and expert peer review, providing freely accessible research to readers. Led by distinguished scientists, the journal supports AAAS's mission by extending Science magazine's capacity to identify and promote significant advances. Evolving digital publishing technologies play a crucial role in advancing AAAS's global mission for science communication and benefitting humankind.