Liu Kuan-Guan, Gao Xue-Mei, Liu Tongyu, Hu Mao-Lin, Jiang De-En
State Key Laboratory of High-efficiency Coal Utilization and Green Chemical Engineering and Ningxia Key Laboratory for Photovoltaic Materials, Ningxia University, Yinchuan, Ningxia 750021, China.
Department of Chemistry, University of California, Riverside, California 92521, United States.
J Am Chem Soc. 2020 Oct 7;142(40):16905-16909. doi: 10.1021/jacs.0c06682. Epub 2020 Sep 24.
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 AgNO under alkaline conditions, yielding a single crystal of [(CH)NH][Ag(pfga)]. The [Ag(pfga)] cluster has a rhombohedral Ag 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) configuration and explains the optical absorption of the cluster in the visible region as the transition from 1S to 1P orbital. The [Ag(pfga)] cluster emits bright green-yellow light in THF 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.
我们报道了首个全羧酸盐保护的超原子银纳米团簇的合成与结构。它是通过在碱性条件下加热全氟戊二酸和硝酸银的二甲基甲酰胺溶液制备而成，得到了[(CH)NH][Ag(pfga)]的单晶。[Ag(pfga)]团簇具有一个菱面体银核，其每个面都由一个二价阴离子全氟戊二酸酯（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由于(1S)构型中超原子轨道的壳层闭合而具有稳定性，并解释了该团簇在可见光区域的光吸收是从1S到1P轨道的跃迁。[Ag(pfga)]团簇在四氢呋喃溶液中发出亮绿黄色光，在固态时发出亮橙色光。这项工作为利用广泛可得的羧酸合成具有吸引人特性的原子精确银团簇打开了大门。
