title: Ultraviolet Photodissociation of Selected Gold Clusters: Ultraefficient Unstapling and Ligand Stripping of Au25(pMBA)18and Au36(pMBA)24.
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)18and 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.
authors.affiliation: Department of Physics and Astronomy, The University of Texas at San Antonio , San Antonio, Texas 78249, United States.
authors.forename: David M
authors.identifier: http://orcid.org/0000-0003-2757-447X
authors.initials: DM
authors.lastname: Black
authors.affiliation: Department of Chemistry, The University of Texas at Austin , Austin, Texas 78712, United States.
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Crittenden
authors.affiliation: Department of Chemistry, The University of Texas at Austin , Austin, Texas 78712, United States.
authors.forename: Jennifer S
authors.identifier: http://orcid.org/0000-0003-3207-0217
authors.initials: JS
authors.lastname: Brodbelt
authors.affiliation: Department of Physics and Astronomy, The University of Texas at San Antonio , San Antonio, Texas 78249, United States.
authors.forename: Robert L
authors.initials: RL
authors.lastname: Whetten