4.6 Article

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

Journal

CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 22, Pages 8262-8270

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201406002

Keywords

azo compounds; density functional calculations; isomerisation; photochromism; ruthenium

Funding

  1. MESR
  2. GENCI (Grand Equipement National de Calcul Intensif) [2013-[x2013080649]]

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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.

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