Toward Understanding the Correlation between the Charge States and the Core Structures in Thiolate-Protected Gold Nanoclusters
Toward Understanding the Correlation between the Charge States and the Core Structures in Thiolate-Protected Gold Nanoclusters
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DOI：
10.1021/acs.jpclett.2c01306
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发表时间：
2022-06-23
影响因子：
5.7
通讯作者：
Wang, Endong
中科院分区：
文献类型：
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作者：
Liu, Yuxin;Han, Wenhua;Wang, Endong
硫醇盐保护的金纳米团簇的电荷状态通过影响价电子的数目而对其稳定性起着至关重要的作用。然而，AuNCs的电荷态的起源尚未完全理解。在此，通过满足大统一模型（GUM）中duet规则推导的Au-3（2 e）和Au-4（2 e）基本块，对实质晶体结构的分析表明，AuNC的电荷状态可以与其核心结构堆积相关，尤其是与Au-3（2 e）基本块的数量相关。此外，借助于Au-3（2 e）块在定制价电子布居中的作用，通过可控地指定核中Au-3（2 e）的确切数目，预测了三种新的AuNC，包括Au-18（SCH 3）（14）、Au-30（SCH 3）（20）和[Au-30（SCH 3）（21）]（-）。研究结果表明，GUM可以通过电子计数规则，在团簇电荷态、团簇内核结构和外部配体脱离之间架起差距的桥梁。
The charge states of thiolate-protected gold nanoclusters (AuNCs) are vital to their stabilities through affecting the number of the valence electrons. However, the origin of the charge states of AuNCs has not been fully understood yet. Herein, through fulfilling the duet-rule derived Au-3(2e) and Au-4(2e) elementary blocks in the grand unified model (GUM), analysis on the substantial crystal structures indicates the charge states of AuNCs can correlate with their core structural packing, especially the number of Au-3(2e) elementary blocks. In addition, aided by the Au-3(2e) block's role in tailoring the population of valence electron, three new AuNCs including Au-18(SCH3)(14), Au-30(SCH3)(20), and [Au-30(SCH3)(21)](-) are predicted through controllably specifying the exact number of Au-3(2e) in the core. This work shows that GUM can bridge the gap among the charge states of the cluster, the inner core structure of the cluster, and the detachment of outer ligands via the electron counting rule.