Photoisomerisation in Aminoazobenzene-Substituted Ruthenium(II) Tris(bipyridine) Complexes: Influence of the Conjugation Pathway

Transition‐metal complexes containing stimuli‐responsive systems are attractive for applications in optical devices, photonic memory, photosensing, as well as luminescence imaging. Amongst them, photochromic metal complexes offer the possibility of combining the specific properties of the metal cent...

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Bibliographic Details
Published in:Chemistry : a European journal 2015-05, Vol.21 (22), p.8262-8270
Main Authors: Amar, Anissa, Savel, Paul, Akdas-Kilig, Huriye, Katan, Claudine, Meghezzi, Hacène, Boucekkine, Abdou, Malval, Jean-Pierre, Fillaut, Jean-Luc
Format: Article
Language:English
Subjects:
Acceptors (electronic)
azo compounds
Backbone
Cations
Chemical Sciences
Chemistry
Coordination chemistry
Coordination compounds
density functional calculations
Electronics
isomerisation
Ligands
Modulation
photochromism
Ruthenium
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Summary:Transition‐metal complexes containing stimuli‐responsive systems are attractive for applications in optical devices, photonic memory, photosensing, as well as luminescence imaging. Amongst them, photochromic metal complexes offer the possibility of combining the specific properties of the metal centre and the optical response of the photochromic group. The synthesis, the electrochemical properties and the photophysical characterisation of a series of donor–acceptor azobenzene derivatives that possess bipyridine groups connected to a 4‐dialkylaminoazobenzene moiety through various linkers are presented. DFT and TD‐DFT calculations were performed to complement the experimental findings and contribute to their interpretation. The position and nature of the linker (ethynyl, triazolyl, none) were engineered and shown to induce different electronic coupling between donor and acceptor in ligands and complexes. This in turn led to strong modulations in terms of photoisomerisation of the ligands and complexes. Making the switch: Engineering of azobenzene‐containing bipyridine ligands leads to strong modulation of the photoisomerisation properties of their ruthenium heteroleptic complexes (see picture; MLCT=metal‐to‐ligand charge transfer). An electronic communication involving the ruthenium cation disfavours the photoisomerisation; in contrast, extending the molecular backbone from the bipyridine to the azobenzene with ethynyl or triazolyl linkers results in photoswitchable complexes.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201406002