6533b82efe1ef96bd1293149

RESEARCH PRODUCT

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

Gao LiGao LiHannu HäkkinenJunhui WangSami MalolaKaifeng WuZhaoxian QinZhaoxian QinSachil Sharma

subject

Materials science010405 organic chemistryElectrospray ionizationTrimer010402 general chemistry01 natural sciencesDissociation (chemistry)0104 chemical sciencesCrystallographyFragmentation (mass spectrometry)Ultrafast laser spectroscopyCluster (physics)General Materials SciencePhysical and Theoretical ChemistryAbsorption (chemistry)Spectroscopy

description

We present the photoinduced size/structure transformation of [Au37-xAgx(PPh3)13Cl10]3+ (M37) into [Au25-yAgy(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.

yearjournalcountryeditionlanguage
2021-11-04The Journal of Physical Chemistry Letters
https://doi.org/10.1021/acs.jpclett.1c02863