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Anomalous Light‐Induced Spin‐State Switching for Iron(II) Spin‐Crossover Molecules in Direct Contact with Metal Surfaces
Author(s) -
Zhang Luqiong,
Tong Yongfeng,
Kelai Massine,
Bellec Amandine,
Lagoute Jérôme,
Chacon Cyril,
Girard Yann,
Rousset Sylvie,
Boillot MarieLaure,
Rivière Eric,
Mallah Talal,
Otero Edwige,
Arrio MarieAnne,
Sainctavit Philippe,
Repain Vincent
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202003896
Subject(s) - spin crossover , spin states , excited state , chemistry , metal , molecule , spin (aerodynamics) , triplet state , molecular physics , condensed matter physics , materials science , atomic physics , crystallography , inorganic chemistry , physics , organic chemistry , thermodynamics
Light‐induced spin‐state switching is one of the most attractive properties of spin‐crossover materials. In bulk, low‐spin (LS) to high‐spin (HS) conversion via the light‐induced excited spin‐state trapping (LIESST) effect may be achieved with a visible light, while the HS‐to‐LS one (reverse‐LIESST) requires an excitation in the near‐infrared range. Now, it is shown that those phenomena are strongly modified at the interface with a metal. Indeed, an anomalous spin conversion is presented from HS state to LS state under blue light illumination for Fe II spin‐crossover molecules that are in direct contact with metallic (111) single‐crystal surfaces (copper, silver, and gold). To interpret this anomalous spin‐state switching, a new mechanism is proposed for the spin conversion based on the light absorption by the substrate that can generate low energy valence photoelectrons promoting molecular vibrational excitations and subsequent spin‐state switching at the molecule–metal interface.