Plasser_ejic.201901304.pdf (3.92 MB)
Multi-tier electronic structure analysis of Sita's Mo and W complexes capable of thermal or photochemical N2 splitting
journal contribution
posted on 2020-03-06, 08:54 authored by Severine Rupp, Felix PlasserFelix Plasser, Vera KrewaldAn emerging approach for the activation of the nitrogen molecule is the light‐driven splitting of the N‐N bond . Less than ten examples for complexes capable of N 2 photoactivation are currently known, and the underlying photophysical and photochemical processes after light absorption are largely unresolved. All complexes have a central [M(μ‐η 1 :η 1 ‐N 2 )M] unit with symmetric ligand spheres around the metals. For several of these complexes, small modifications of the ligand sphere result in thermal rather than photochemical activity. Herein, we analyse the electronic structures and computed UV‐vis spectra of four complexes: two thermally and two photochemically active complexes, each either involving Mo or W. The analysis of electronic structures and spectra is based on the molecular orbitals, difference densities and the charge‐transfer numbers provided by TheoDORE. We find that the spectra of the photochemically active complexes contain excitations with more ligand‐to‐metal charge‐transfer character and higher intensity, providing a plausible explanation for light‐induced nitrogen splitting.
History
School
- Science
Department
- Chemistry
Published in
European Journal of Inorganic ChemistryVolume
2020Issue
15-16Pages
1506-1518Publisher
WileyVersion
- AM (Accepted Manuscript)
Rights holder
© WILEY‐VCH Verlag GmbH & Co. KGaA, WeinheimPublisher statement
This is an Open Access Article. It is published by Elsevier under the Creative Commons Attribution 4.0 Unported Licence (CC BY). Full details of this licence are available at: http://creativecommons.org/licenses/by/4.0/Acceptance date
2020-03-04Publication date
2020-03-20Copyright date
2020ISSN
1434-1948eISSN
1099-0682Publisher version
Language
- en