Ultraviolet Photodissociation of Selected Gold Clusters: Ultraefficient Unstapling and Ligand Stripping of Au25(pMBA)18 and Au36(pMBA)24

David M. Black, Christopher M. Crittenden, Jennifer S. Brodbelt, Robert L. Whetten

Research output: Contribution to journalLetterpeer-review

21 Scopus citations

Abstract

We report the first results of ultraviolet photodissociation (UVPD) mass spectrometry of trapped monolayer-protected cluster (MPC) ions generated by electrospray ionization. Gold clusters Au25(pMBA)18 and Au36(pMBA)24 (pMBA = para-mercaptobenzoic acid) were analyzed in both the positive and negative modes. Whereas activation methods including collisional- and electron-based methods produced relatively few fragment ions, even a single ultraviolet pulse (at λ = 193 nm) caused extensive fragmentation of the positively charged clusters. Upon photoactivation using a low number of laser pulses, the staple motifs of both clusters were cleaved and stripped of the protecting ligand portions without removal of any contained gold atoms. This striking process involved Au-S and C-S bond cleavages via a pathway made possible by 6.4 eV photon absorption. Monomer evaporation (neutral gold atom loss) occurred upon exposure to multiple pulses, resulting in a size series of bare gold-cluster ions. All tandem mass spectrometric methods produced the singly charged ring tetramer ion, [Au4(pMBA)4 + Na]+, for each cluster.

Original languageEnglish (US)
Pages (from-to)1283-1289
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume8
Issue number6
DOIs
StatePublished - Mar 16 2017
Externally publishedYes

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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