TY - JOUR
T1 - Ultraviolet Photodissociation of Selected Gold Clusters
T2 - Ultraefficient Unstapling and Ligand Stripping of Au25(pMBA)18 and Au36(pMBA)24
AU - Black, David M.
AU - Crittenden, Christopher M.
AU - Brodbelt, Jennifer S.
AU - Whetten, Robert L.
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/3/16
Y1 - 2017/3/16
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.jpclett.7b00442
DO - 10.1021/acs.jpclett.7b00442
M3 - Letter
C2 - 28234006
AN - SCOPUS:85015197939
SN - 1948-7185
VL - 8
SP - 1283
EP - 1289
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 6
ER -