All-Carboxylate-Protected Superatomic Silver Nanocluster with an Unprecedented Rhombohedral Ag8 Core
All-Carboxylate-Protected Superatomic Silver Nanocluster with an Unprecedented Rhombohedral Ag8 Core
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DOI：
10.1021/jacs.0c06682
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发表时间：
2020-10-07
影响因子：
15
通讯作者：
Jiang, De-En
中科院分区：
文献类型：
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作者：
Liu, Kuan-Guan;Gao, Xue-Mei;Jiang, De-En
报道了第一个全羧酸根保护的超原子银纳米团簇的合成和结构。通过在碱性条件下加热全氟谷氨酸和AgNO 3的二甲基甲酰胺溶液制备，得到[（CH 3）（2）NH 2]（6）[Ag-8（pfga）（6）]单晶。[Ag-8（pfga）（6）]（6）（-）簇合物具有菱形Ag-8（6+）核，其每个面由一个双阴离子全氟戊二酸（pfga）配体保护。密度泛函理论的电子结构分析证实了这种双电子团簇的稳定性是由于（1 S）（2）构型中超原子轨道的壳层闭合，并解释了团簇在可见光区的光吸收是从1 S到1 P轨道的跃迁。[Ag-8（pfga）（6）]（6-）团簇在THE溶液中发出明亮的绿黄色光，在固态时发出明亮的橙子光。这项工作打开了大门，使用广泛可用的羧酸合成原子精确的银簇的吸引力的性能。
We report the synthesis and structure of the first all-carboxylate-protected superatomic silver nanocluster. It was prepared by heating a dimethylformamide solution of perfluoroglutaric acid and AgNO3 under alkaline conditions, yielding a single crystal of [(CH3)(2)NH2](6)[Ag-8(pfga)(6)]. The [Ag-8(pfga)(6)](6)(-) cluster has a rhombohedral Ag-8(6+) core, with each of its faces protected by one dianionic perfluoroglutarate (pfga) ligand. Electronic-structure analysis from density functional theory confirms the stability of this two-electron cluster due to the shell closing of the superatomic orbital in the (1S)(2) configuration and explains the optical absorption of the cluster in the visible region as the transition from 1S to 1P orbital. The [Ag-8(pfga)(6)](6-) cluster emits bright green-yellow light in THE solution and bright orange light in the solid state. This work opens the door to using the widely available carboxylic acids to synthesize atomically precise Ag clusters of attractive properties.