Transient metal-centered states mediate isomerization of a photochromic ruthenium-sulfoxide complex - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Nature Communications Année : 2018

Transient metal-centered states mediate isomerization of a photochromic ruthenium-sulfoxide complex

Résumé

Ultrafast isomerization reactions underpin many processes in (bio)chemical systems and molecular materials. Understanding the coupled evolution of atomic and molecular structure during isomerization is paramount for control and rational design in molecular science. Here we report transient X-ray absorption studies of the photo-induced linkage isomerization of a Ru-based photochromic molecule. X-ray spectra reveal the spin and valence charge of the Ru atom and provide experimental evidence that metal-centered excited states mediate iso-merization. Complementary X-ray spectra of the functional ligand S atoms probe the nuclear structural rearrangements, highlighting the formation of two metal-centered states with different metal-ligand bonding. These results address an essential open question regarding the relative roles of transient charge-transfer and metal-centered states in mediating pho-toisomerization. Global temporal and spectral data analysis combined with time-dependent density functional theory reveals a complex mechanism for photoisomerization with atomic details of the transient molecular and electronic structure not accessible by other means.
Fichier principal
Vignette du fichier
ru_oso_trxas_naturecommun2018.pdf (1.02 Mo) Télécharger le fichier
Origine : Fichiers éditeurs autorisés sur une archive ouverte
Loading...

Dates et versions

hal-01814707 , version 1 (15-06-2020)

Identifiants

Citer

Amy A. Cordones, Jae Hyuk Lee, Kiryong Hong, Hana Cho, Komal Garg, et al.. Transient metal-centered states mediate isomerization of a photochromic ruthenium-sulfoxide complex. Nature Communications, 2018, 9, pp.1989. ⟨10.1038/s41467-018-04351-0⟩. ⟨hal-01814707⟩
51 Consultations
47 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More