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

Journal Article · · Nature Communications
ORCiD logo [1];  [2]; ORCiD logo [3];  [3];  [4]; ORCiD logo [5];  [6]; ORCiD logo [7];  [8]; ORCiD logo [9]
  1. Stanford Univ., Menlo Park, CA (United States)
  2. Pohang Accelerator Lab., Pohang (Republic of Korea)
  3. Korea Research Institute of Standards and Science, Daejeon (Republic of Korea)
  4. Ohio Univ., Athens, OH (United States)
  5. CNRS et Univ. de Toulouse, Toulouse (France)
  6. Ohio Univ., Athens, OH (United States); The Univ. of New Mexico, Albuquerque, NM (United States)
  7. Univ. of Hamburg, Hamburg (Germany); Max Planck Institute for the Structure and Dynamics of Matter and Center for Free-Electron Laser Science, Hamburg (Germany)
  8. Stanford Univ., Menlo Park, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  9. Pusan National Univ., Busan (Republic of Korea)
+ Show Author Affiliations

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. As a result, 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.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1458733
Journal Information:
Nature Communications, Vol. 9, Issue 1; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 24 works
Citation information provided by
Web of Science

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Cited By (3)

Chemical interactions and dynamics with femtosecond X-ray spectroscopy and the role of X-ray free-electron lasers journal April 2019
Multistep Photochemical Reactions of Polypyridine-Based Ruthenium Nitrosyl Complexes in Dimethylsulfoxide journal May 2020
Chemical interactions and dynamics with femtosecond X-ray spectroscopy and the role of X-ray free-electron lasers text January 2019

Figures / Tables (5)

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Fig. 3(p. 4)figure Fig. 3
Fig. 4(p. 6)figure Fig. 4
Fig. 5(p. 7)figure Fig. 5

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY