A photoinduced mixed valence photoswitch

Cotic A, Cerfontaine S, Slep LD, Elias B, Troian-Gautier L, Cadranel A (2022)

Publication Type: Journal article

Publication year: 2022

Journal

Physical Chemistry Chemical Physics Royal Society of Chemistry

DOI: 10.1039/d2cp01791a

Abstract

The ground state and photoinduced mixed valence states (GSMV and PIMV, respectively) of a dinuclear (Dp(4+)) 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 H-DA similar to 450 cm(-1) in the PIMV state, whereas the electrochemically generated GSMV state showed H-DA similar to 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 degrees and 4 degrees 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 Dp(4+) a competitive candidate for photoswitching applications. A novel strategy to design photoinduced charge transfer molecular switches is proposed.

Authors with CRIS profile

Alejandro Cadranel Lehrstuhl für Physikalische Chemie I

Involved external institutions

Universidad de Buenos Aires (UBA) / University of Buenos Aires AR Argentina (AR) Université Catholique de Louvain (UCL) BE Belgium (BE)

How to cite

APA:

Cotic, A., Cerfontaine, S., Slep, L.D., Elias, B., Troian-Gautier, L., & Cadranel, A. (2022). A photoinduced mixed valence photoswitch. Physical Chemistry Chemical Physics. https://doi.org/10.1039/d2cp01791a

MLA:

Cotic, Agustina, et al. "A photoinduced mixed valence photoswitch." Physical Chemistry Chemical Physics (2022).

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