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Site-specific doping of silver atoms into a Au25 nanocluster as directed by ligand binding preferences.

ABSTRACT: For the first time site-specific doping of silver into a spherical Au25 nanocluster has been achieved in [Au19Ag6(MeOPhS)17(PPh3)6] (BF4)2 (Au19Ag6) through a dual-ligand coordination strategy. Single crystal X-ray structural analysis shows that the cluster has a distorted centered icosahedral Au@Au6Ag6 core of D 3 symmetry, in contrast to the I h Au@Au12 kernel in the well-known [Au25(SR)18]- (R = CH2CH2Ph). An interesting feature is the coexistence of [Au2(SPhOMe)3] dimeric staples and [P-Au-SPhOMe] semi-staples in the title cluster, due to the incorporation of PPh3. The observation of only one double-charged peak in ESI-TOF-MS confirms the ordered doping of silver atoms. Au19Ag6 is a 6e system showing a distinct absorption spectrum from [Au25(SR)18]-, that is, the HOMO-LUMO transition of Au19Ag6 is optically forbidden due to the P character of the superatomic frontier orbitals.

SUBMITTER: Shi WQ 

PROVIDER: S-EPMC9093122 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature

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Site-specific doping of silver atoms into a Au<sub>25</sub> nanocluster as directed by ligand binding preferences.

Shi Wan-Qi WQ   Guan Zong-Jie ZJ   Li Jiao-Jiao JJ   Han Xu-Shuang XS   Wang Quan-Ming QM  

Chemical science 20220315 18

For the first time site-specific doping of silver into a spherical Au<sub>25</sub> nanocluster has been achieved in [Au<sub>19</sub>Ag<sub>6</sub>(MeOPhS)<sub>17</sub>(PPh<sub>3</sub>)<sub>6</sub>] (BF<sub>4</sub>)<sub>2</sub> (Au<sub>19</sub>Ag<sub>6</sub>) through a dual-ligand coordination strategy. Single crystal X-ray structural analysis shows that the cluster has a distorted centered icosahedral Au@Au<sub>6</sub>Ag<sub>6</sub> core of <i>D</i> <sub>3</sub> symmetry, in contrast to the <i>I  ...[more]

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