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@ARTICLE{Schubert:459413,
author = {Schubert, Kaja and Schwob, Lucas and Dörner, Simon and
Girod, Marion and MacAleese, Luke and Pieterse, Cornelius L.
and Schlathölter, Thomas and Techert, Simone and Bari,
Sadia},
title = {{I}onization and photofragmentation of isolated
metalloporphyrin cations investigated by {VUV} action
spectroscopy},
journal = {Chemistry - a European journal},
volume = {27},
number = {48},
issn = {0947-6539},
address = {Weinheim},
publisher = {Wiley-VCH},
reportid = {PUBDB-2021-02558},
pages = {12371 - 12379},
year = {2021},
abstract = {We investigated the photoionization and fragmentation of
isolated metal protoporphyrin IX cations (MPPIX+ with M=Fe,
Co, Zn) by means of vacuum-ultraviolet (VUV) action
spectroscopy in the energy range of 8.5–35 eV.
Experiments were carried out in the gas phase by interfacing
an electrospray ionization tandem mass spectrometer with a
synchrotron beamline. The mass spectra and partial ion
yields show that photoexcitation of the precursor ions
predominantly leads to .CH$_2$COOH radical side-chain losses
of the macrocycle with additional methyl radical (.CH$_3$)
side-chain losses. Ionization, in contrast, leads to the
formation of the intact ionized precursor and various doubly
charged fragments which are mostly due to side-chain
cleavages. Although statistical fragmentation dominates, we
found evidence for non-statistical processes such as new
fragments involving for example single and double H2O
losses, indicating that different relaxation mechanisms are
at play upon photoionization compared to photoexcitation.
The measured ionization energies were 9.6±0.2 eV,
9.4±0.2 eV and 9.6±0.2 eV for FePPIX$^+$, CoPPIX$^+$
and ZnPPIX$^+$, respectively.},
cin = {FS-SCS},
ddc = {540},
cid = {I:(DE-H253)FS-SCS-20131031},
pnm = {633 - Life Sciences – Building Blocks of Life: Structure
and Function (POF4-633) / DFG project 28586557 - SFB 755:
Photonische Abbildungen auf der Nanometerskala (28586557)},
pid = {G:(DE-HGF)POF4-633 / G:(GEPRIS)28586557},
experiment = {EXP:(DE-MLZ)External-20140101},
typ = {PUB:(DE-HGF)16},
pubmed = {34137472},
UT = {WOS:000672694700001},
doi = {10.1002/chem.202101515},
url = {https://bib-pubdb1.desy.de/record/459413},
}