Photo-Induced Cluster-to-Cluster Transformation of [Au37- xAgx(PPh3)13Cl10]3+ into [Au25- yAgy(PPh3)10Cl8]+: Fragmentation of a Trimer of 8-Electron Superatoms by Light

Zhaoxian Qin; Junhui Wang; Sachil Sharma; Sami Malola; Kaifeng Wu; Hannu Häkkinen; Gao Li

doi:10.1021/acs.jpclett.1c02863

Photo-Induced Cluster-to-Cluster Transformation of [Au_{37- x}Ag_x(PPh₃)₁₃Cl₁₀]³⁺ into [Au_{25- y}Ag_y(PPh₃)₁₀Cl₈]⁺: Fragmentation of a Trimer of 8-Electron Superatoms by Light

J Phys Chem Lett. 2021 Nov 11;12(44):10920-10926. doi: 10.1021/acs.jpclett.1c02863. Epub 2021 Nov 4.

Authors

Zhaoxian Qin^{1

2}, Junhui Wang³, Sachil Sharma¹, Sami Malola⁴, Kaifeng Wu³, Hannu Häkkinen⁴, Gao Li^{1

2}

Affiliations

¹ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P.R. China.
² University of Chinese Academy of Sciences, Beijing 100049, China.
³ State Key Laboratory of Molecular Reaction Dynamics and Dynamics Research Center for Energy and Environmental Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 Liaoning, China.
⁴ Departments of Physics and Chemistry, Nanoscience Center, University of Jyväskylä, FI-40014 Jyväskylä, Finland.

PMID: 34734733
DOI: 10.1021/acs.jpclett.1c02863

Abstract

We present the photoinduced size/structure transformation of [Au_37-xAg_x(PPh₃)₁₃Cl₁₀]³⁺ (M37) into [Au_25-yAg_y(PPh₃)₁₀Cl₈]⁺ (M25) cluster. Single-crystal X-ray diffraction revealed that M37 has a tri-icosahedron M₃₆ metal core assembled via the fusion of three Au₇Ag₆ icosahedrons in a cyclic fashion and that the M₃₆ core is further protected by phosphine and chloride ligands. The M37 cluster is found to be highly sensitive toward ambient light, and the M37 → M25 transition is observed with 530 nm irradiation, monitored by time-dependent UV-vis spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and femtosecond transient absorption spectroscopy. Linear-response time-dependent DFT calculations indicated that the strong absorption of the M37 cluster close to 500 nm induces an antibonding-type configuration in the induced electron density within the plane of the three 8-electron systems, possibly promoting dissociation of one of the 8-electron superatoms. This theoretical result supports the experimental observation of the sensitivity of the M37 → M25 transition to 530 nm irradiation.