Redox-triggered chiroptical switching activity of ruthenium(III)-bis-(β-diketonato) complexes bearing a bipyridine-helicene ligand

Chirality
N SalehJ Crassous

Abstract

The charged, electroactive bipyridine-helicene-ruthenium(III) complex [4].+ ,PF6- has been prepared from 3-(2-pyridyl)-4-aza[6]helicene and a Ru-bis-(β-diketonato)-bis-acetonitrile precursor (β-diketonato: 2,2,6,6-tetramethyl-3,5-heptanedionato). Its chiroptical properties (electronic circular dichroism and optical rotation) were studied both experimentally and theoretically and suggest the presence of 2 diastereoisomers, namely (P,Δ)- and (P,Λ)-[4].+ ,PF6- (denoted jointly as (P,Δ*)-[4].+ ,PF6- ) and their mirror-images (M,Λ)- and (M,Δ)-[4].+ ,PF6- ((M,Δ*)-[4].+ ,PF6- ). The electrochemical reduction of (P,Δ*)-[4].+ ,PF6- to neutral complex (P,Δ*)-4 was performed and revealed strong changes in the UV-vis and electronic circular dichroism spectra. A reversible redox-triggered chiroptical switching process was then achieved.

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Jun 15, 1986·Physical Review. B, Condensed Matter·J P Perdew
Jun 27, 2014·Accounts of Chemical Research·Jochen Autschbach, Monika Srebro
Oct 7, 2015·Chemistry : a European Journal·Monika SrebroJeanne Crassous
Apr 8, 2016·Chemical Communications : Chem Comm·Helena IslaJeanne Crassous
Dec 3, 2016·Chemical Communications : Chem Comm·J-K Ou-YangB Le Guennic
May 4, 2017·Annual Review of Physical Chemistry·Monika Srebro-Hooper, Jochen Autschbach

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Citations

Mar 30, 2019·The Journal of Organic Chemistry·Helena IslaJeanne Crassous
May 3, 2019·The Journal of Physical Chemistry. a·Tal Aharon, Marco Caricato
Oct 5, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Jun YoshidaHisako Sato
Oct 23, 2021·Angewandte Chemie·Jeffrey S S K Formen, Christian Wolf

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