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Optically Controlled Electron Transfer in a Re I Complex
Author(s) -
Rohwer Egmont J.,
Geng Yan,
Akbarimoosavi Maryam,
Daku Latévi M. Lawson,
Aleveque Olivier,
Levillain Eric,
Hauser Jürg,
Cannizzo Andrea,
Häner Robert,
Decurtins Silvio,
Stanley Robert J.,
Feurer Thomas,
Liu ShiXia
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202005125
Subject(s) - ultrafast laser spectroscopy , intramolecular force , photochemistry , spectroscopy , absorption (acoustics) , absorption spectroscopy , electron transfer , photocurrent , materials science , homo/lumo , chemistry , analytical chemistry (journal) , chemical physics , optoelectronics , stereochemistry , molecule , optics , physics , organic chemistry , quantum mechanics , composite material
Ultrafast optical control of intramolecular charge flow was demonstrated, which paves the way for photocurrent modulation and switching with a highly wavelength‐selective ON/OFF ratio. The system that was explored is a fac ‐[Re(CO) 3 (TTF‐DPPZ)Cl] complex, where TTF‐DPPZ=4’,5’‐bis(propylthio)tetrathiafulvenyl[ i ]dipyrido[3,2‐ a :2’,3’‐ c ]phenazine. DFT calculations and AC‐Stark spectroscopy confirmed the presence of two distinct optically active charge‐transfer processes, namely a metal‐to‐ligand charge transfer (MLCT) and an intra‐ligand charge transfer (ILCT). Ultrafast transient absorption measurements showed that the ILCT state decays in the ps regime. Upon excitation to the MLCT state, only a long‐lived 3 MLCT state was observed after 80 ps. Remarkably, however, the bleaching of the ILCT absorption band remained as a result of the effective inhibition of the HOMO–LUMO transition.