Jump to main content
Jump to site search

Issue 7, 2017
Previous Article Next Article

Comparison of structural dynamics and coherence of d–d and MLCT light-induced spin state trapping

Author affiliations

Abstract

Light-induced excited spin state trapping (LIESST) in FeII spin-crossover systems is a process that involves the switching of molecules from low (LS, S = 0) to high spin (HS, S = 2) states. The direct LS-to-HS conversion is forbidden by selection rules, and LIESST involves intermediate states such as 1,3MLCT or 1,3T. The intersystem crossing sequence results in an HS state, structurally trapped by metal–ligand bond elongation through the coherent activation and damping of molecular breathing. The ultrafast dynamics of this process has been investigated in FeN6 ligand field systems, under MLCT excitation. Herein, we studied LIESST in an FeIIN4O2 spin-crossover material of lower symmetry, which allowed for quite intense and low-energy shifted d–d bands. By combining ab initio DFT and TD-DFT calculations and fs optical absorption measurements, we demonstrated that shorter intermediates enhanced coherent structural dynamics, and d–d excitation induced faster LS-to-HS switching, compared to MLCT.

Graphical abstract: Comparison of structural dynamics and coherence of d–d and MLCT light-induced spin state trapping

Back to tab navigation

Supplementary files

Publication details

The article was received on 22 Dec 2016, accepted on 19 Apr 2017 and first published on 24 Apr 2017


Article type: Edge Article
DOI: 10.1039/C6SC05624E
Citation: Chem. Sci., 2017,8, 4978-4986
  • Open access: Creative Commons BY license
  •   Request permissions

    Comparison of structural dynamics and coherence of d–d and MLCT light-induced spin state trapping

    S. Zerdane, L. Wilbraham, M. Cammarata, O. Iasco, E. Rivière, M.-L. Boillot, I. Ciofini and E. Collet, Chem. Sci., 2017, 8, 4978
    DOI: 10.1039/C6SC05624E

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements