TY - JOUR
T1 - Ultrafast Photofragmentation of Ln(hfac)3 with a Proposed Mechanism for forming High Mass Fluorinated Products
AU - Chen, Jiangchao
AU - Xing, Xi
AU - Rey-de-Castro, Roberto
AU - Rabitz, Herschel
N1 - Publisher Copyright:
© 2020, The Author(s).
PY - 2020/12/1
Y1 - 2020/12/1
N2 - The photo-induced dissociative-ionization of lanthanide complexes Ln(hfac)3 (Ln = Pr, Er, Yb) is studied using intense ultrafast transform limited (TL) and linearly chirped laser pulses in a time-of-flight (TOF) mass spectrometry setup. Various fluorine and Ln-containing high-mass fragments were observed in this experiment, including the molecular parent ion, which have not been seen with previous studies relying on relatively long-duration laser pulses (i.e., ns or longer). These new high-mass observations provide important formerly missing information for deducing a set of photo-fragmentation mechanistic pathways for Ln(hfac)3. An overall ultrafast control mechanism is proposed by combining insights from earlier studies and the fragments observed in this research to result in three main distinct photo-fragmentation processes: (a) ligand-metal charge transfer, (b) CF3 elimination, and (c) C-C bond rotation processes. We conclude that ultrafast dissociative-ionization could be a promising technique for generating high-mass fragments for potential use in material science applications.
AB - The photo-induced dissociative-ionization of lanthanide complexes Ln(hfac)3 (Ln = Pr, Er, Yb) is studied using intense ultrafast transform limited (TL) and linearly chirped laser pulses in a time-of-flight (TOF) mass spectrometry setup. Various fluorine and Ln-containing high-mass fragments were observed in this experiment, including the molecular parent ion, which have not been seen with previous studies relying on relatively long-duration laser pulses (i.e., ns or longer). These new high-mass observations provide important formerly missing information for deducing a set of photo-fragmentation mechanistic pathways for Ln(hfac)3. An overall ultrafast control mechanism is proposed by combining insights from earlier studies and the fragments observed in this research to result in three main distinct photo-fragmentation processes: (a) ligand-metal charge transfer, (b) CF3 elimination, and (c) C-C bond rotation processes. We conclude that ultrafast dissociative-ionization could be a promising technique for generating high-mass fragments for potential use in material science applications.
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U2 - 10.1038/s41598-020-64015-2
DO - 10.1038/s41598-020-64015-2
M3 - Article
C2 - 32341431
AN - SCOPUS:85084010159
SN - 2045-2322
VL - 10
JO - Scientific reports
JF - Scientific reports
IS - 1
M1 - 7066
ER -