TY - JOUR
T1 - Transient metal-centered states mediate isomerization of a photochromic ruthenium-sulfoxide complex
AU - Cordones, Amy A.
AU - Lee, Jae Hyuk
AU - Hong, Kiryong
AU - Cho, Hana
AU - Garg, Komal
AU - Boggio-Pasqua, Martial
AU - Rack, Jeffrey J.
AU - Huse, Nils
AU - Schoenlein, Robert W.
AU - Kim, Tae Kyu
N1 - Publisher Copyright:
© 2018 The Author(s).
PY - 2018/12/1
Y1 - 2018/12/1
N2 - 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 isomerization. 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 photoisomerization. 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.
AB - 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 isomerization. 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 photoisomerization. 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.
UR - http://www.scopus.com/inward/record.url?scp=85047211284&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85047211284&partnerID=8YFLogxK
U2 - 10.1038/s41467-018-04351-0
DO - 10.1038/s41467-018-04351-0
M3 - Article
C2 - 29777157
AN - SCOPUS:85047211284
SN - 2041-1723
VL - 9
JO - Nature communications
JF - Nature communications
IS - 1
M1 - 1989
ER -