Issue 7, 2017

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

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

Supplementary files

Article information

Article type
Edge Article
Submitted
22 Dec 2016
Accepted
19 Apr 2017
First published
24 Apr 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 4978-4986

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. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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