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Multi-tier electronic structure analysis of Sita's Mo and W complexes capable of thermal or photochemical N2 splitting

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journal contribution
posted on 06.03.2020 by Severine Rupp, Felix Plasser, Vera Krewald
An 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 Chemistry

Volume

2020

Issue

15-16

Pages

1506-1518

Publisher

Wiley

Version

AM (Accepted Manuscript)

Rights holder

© WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim

Publisher 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

04/03/2020

Publication date

2020-03-20

Copyright date

2020

ISSN

1434-1948

eISSN

1099-0682

Language

en

Depositor

Dr Felix Plasser. Deposit date: 5 March 2020

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