skip to main content

DOE PAGESDOE PAGES

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

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.
Authors:
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)
Publication Date:
Grant/Contract Number:
AC02-76SF00515
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1458733

Cordones, Amy A., Lee, Jae Hyuk, Hong, Kiryong, Cho, Hana, Garg, Komal, Boggio-Pasqua, Martial, Rack, Jeffrey J., Huse, Nils, Schoenlein, Robert W., and Kim, Tae Kyu. Transient metal-centered states mediate isomerization of a photochromic ruthenium-sulfoxide complex. United States: N. p., Web. doi:10.1038/s41467-018-04351-0.
Cordones, Amy A., Lee, Jae Hyuk, Hong, Kiryong, Cho, Hana, Garg, Komal, Boggio-Pasqua, Martial, Rack, Jeffrey J., Huse, Nils, Schoenlein, Robert W., & Kim, Tae Kyu. Transient metal-centered states mediate isomerization of a photochromic ruthenium-sulfoxide complex. United States. doi:10.1038/s41467-018-04351-0.
Cordones, Amy A., Lee, Jae Hyuk, Hong, Kiryong, Cho, Hana, Garg, Komal, Boggio-Pasqua, Martial, Rack, Jeffrey J., Huse, Nils, Schoenlein, Robert W., and Kim, Tae Kyu. 2018. "Transient metal-centered states mediate isomerization of a photochromic ruthenium-sulfoxide complex". United States. doi:10.1038/s41467-018-04351-0. https://www.osti.gov/servlets/purl/1458733.
@article{osti_1458733,
title = {Transient metal-centered states mediate isomerization of a photochromic ruthenium-sulfoxide complex},
author = {Cordones, Amy A. and Lee, Jae Hyuk and Hong, Kiryong and Cho, Hana and Garg, Komal and Boggio-Pasqua, Martial and Rack, Jeffrey J. and Huse, Nils and Schoenlein, Robert W. and Kim, Tae Kyu},
abstractNote = {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.},
doi = {10.1038/s41467-018-04351-0},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {5}
}

Works referenced in this record:

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005
  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a