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The electronic structure and deexcitation pathways of an isolated metalloporphyrin ion resolved by metal L-edge spectroscopy

Schubert, Kaja ; Guo, Meiyuan LU ; Atak, Kaan ; Dörner, Simon ; Bülow, Christine ; von Issendorff, Bernd ; Klumpp, Stephan ; Lau, J. Tobias ; Miedema, Piter S. and Schlathölter, Thomas , et al. (2021) In Chemical Science 12(11). p.3966-3976
Abstract

The local electronic structure of the metal-active site and the deexcitation pathways of metalloporphyrins are crucial for numerous applications but difficult to access by commonly employed techniques. Here, we applied near-edge X-ray absorption mass spectrometry and quantum-mechanical restricted active space calculations to investigate the electronic structure of the metal-active site of the isolated cobalt(iii) protoporphyrin IX cation (CoPPIX+) and its deexcitation pathways upon resonant absorption at the cobalt L-edge. The experiments were carried out in the gas phase, thus allowing for control over the chemical state and molecular environment of the metalloporphyrin. The obtained mass spectra reveal that resonant... (More)

The local electronic structure of the metal-active site and the deexcitation pathways of metalloporphyrins are crucial for numerous applications but difficult to access by commonly employed techniques. Here, we applied near-edge X-ray absorption mass spectrometry and quantum-mechanical restricted active space calculations to investigate the electronic structure of the metal-active site of the isolated cobalt(iii) protoporphyrin IX cation (CoPPIX+) and its deexcitation pathways upon resonant absorption at the cobalt L-edge. The experiments were carried out in the gas phase, thus allowing for control over the chemical state and molecular environment of the metalloporphyrin. The obtained mass spectra reveal that resonant excitations of CoPPIX+at the cobalt L3-edge lead predominantly to the formation of the intact radical dication and doubly charged fragments through losses of charged and neutral side chains from the macrocycle. The comparison between experiment and theory shows that CoPPIX+is in a3A2gtriplet ground state and that competing excitations to metal-centred non-bonding and antibonding σ* molecular orbitals lead to distinct deexcitation pathways.

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type
Contribution to journal
publication status
published
subject
in
Chemical Science
volume
12
issue
11
pages
11 pages
publisher
Royal Society of Chemistry
external identifiers
  • scopus:85103346562
  • pmid:34163667
ISSN
2041-6520
DOI
10.1039/d0sc06591a
language
English
LU publication?
yes
id
aee6aef1-6983-40bd-a652-3dac6dc82cb1
date added to LUP
2021-04-08 08:06:29
date last changed
2025-01-13 06:27:42
@article{aee6aef1-6983-40bd-a652-3dac6dc82cb1,
  abstract     = {{<p>The local electronic structure of the metal-active site and the deexcitation pathways of metalloporphyrins are crucial for numerous applications but difficult to access by commonly employed techniques. Here, we applied near-edge X-ray absorption mass spectrometry and quantum-mechanical restricted active space calculations to investigate the electronic structure of the metal-active site of the isolated cobalt(iii) protoporphyrin IX cation (CoPPIX<sup>+</sup>) and its deexcitation pathways upon resonant absorption at the cobalt L-edge. The experiments were carried out in the gas phase, thus allowing for control over the chemical state and molecular environment of the metalloporphyrin. The obtained mass spectra reveal that resonant excitations of CoPPIX<sup>+</sup>at the cobalt L<sub>3</sub>-edge lead predominantly to the formation of the intact radical dication and doubly charged fragments through losses of charged and neutral side chains from the macrocycle. The comparison between experiment and theory shows that CoPPIX<sup>+</sup>is in a<sup>3</sup>A<sub>2g</sub>triplet ground state and that competing excitations to metal-centred non-bonding and antibonding σ* molecular orbitals lead to distinct deexcitation pathways.</p>}},
  author       = {{Schubert, Kaja and Guo, Meiyuan and Atak, Kaan and Dörner, Simon and Bülow, Christine and von Issendorff, Bernd and Klumpp, Stephan and Lau, J. Tobias and Miedema, Piter S. and Schlathölter, Thomas and Techert, Simone and Timm, Martin and Wang, Xin and Zamudio-Bayer, Vicente and Schwob, Lucas and Bari, Sadia}},
  issn         = {{2041-6520}},
  language     = {{eng}},
  number       = {{11}},
  pages        = {{3966--3976}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Chemical Science}},
  title        = {{The electronic structure and deexcitation pathways of an isolated metalloporphyrin ion resolved by metal L-edge spectroscopy}},
  url          = {{http://dx.doi.org/10.1039/d0sc06591a}},
  doi          = {{10.1039/d0sc06591a}},
  volume       = {{12}},
  year         = {{2021}},
}