A photoinduced mixed valence photoswitch
(2022) Physical Chemistry Chemical Physics — Vol. 24, n° 24, p. 15121-15128 (2022)
Files
Cotic_et_al_PCCP_R1.pdf
Open Access - Adobe PDF
- 1.13 MB
Details
- Authors
Cotic, Agustina 
Cerfontaine, Simon Slep, Leonardo D. Cadranel, Alejandro
- Abstract
- The ground state and photoinduced mixed valence states (GSMV and PIMV, respectively) of a dinuclear (Dp4+) ruthenium(II) complex bearing 2,2′-bipyridine ancillary ligands and a 2,2′:4′,4′′:2′′,2′′′-quaterpyridine (Lp) bridging ligand were investigated using femtosecond and nanosecond transient absorption spectroscopy, electrochemistry and density functional theory. It was shown that the electronic coupling between the transiently light-generated Ru(II) and Ru(III) centers is HDA ∼ 450 cm−1 in the PIMV state, whereas the electrochemically generated GSMV state showed HDA ∼ 0 cm−1, despite virtually identical Ru–Ru distances. This stemmed from the changes in dihedral angles between the two bpy moieties of Lp, estimated at 30° and 4° for the GSMV and PIMV states, respectively, consistent with a through-bond rather than a through-space mechanism. Electronic coupling can be turned on by using visible light excitation, making Dp4+ a competitive candidate for photoswitching applications. A novel strategy to design photoinduced charge transfer molecular switches is proposed.
- Affiliations
Citations
Cotic, A., Cerfontaine, S., Slep, L. D., Elias, B., Troian-Gautier, L., & Cadranel, A. (2022). A photoinduced mixed valence photoswitch. Physical Chemistry Chemical Physics, 24(24), 15121-15128. https://doi.org/10.1039/d2cp01791a (Original work published 2022)