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

Amy A. Cordones, Jae Hyuk Lee, Kiryong Hong, Hana Cho, Komal Garg, Martial Boggio-Pasqua, Jeffrey J. Rack, Nils Huse, Robert W. Schoenlein, Tae Kyu Kim

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

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.

Original languageEnglish
Article number1989
JournalNature communications
Volume9
Issue number1
DOIs
Publication statusPublished - 2018 Dec 1

Fingerprint

sulfoxide
Ruthenium
Isomerization
isomerization
ruthenium
Metals
Photoisomerization
X-Rays
Molecular Structure
metals
Molecular structure
molecular structure
Ligands
X rays
Atoms
ligands
x rays
X ray absorption
Excited states
linkages

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)

Cite this

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. In: Nature communications. 2018 ; Vol. 9, No. 1.
@article{d0049d4e284a449cb61931887e649c01,
title = "Transient metal-centered states mediate isomerization of a photochromic ruthenium-sulfoxide complex",
abstract = "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.",
author = "Cordones, {Amy A.} and Lee, {Jae Hyuk} and Kiryong Hong and Hana Cho and Komal Garg and Martial Boggio-Pasqua and Rack, {Jeffrey J.} and Nils Huse and Schoenlein, {Robert W.} and Kim, {Tae Kyu}",
year = "2018",
month = "12",
day = "1",
doi = "10.1038/s41467-018-04351-0",
language = "English",
volume = "9",
journal = "Nature Communications",
issn = "2041-1723",
publisher = "Nature Publishing Group",
number = "1",

}

Cordones, AA, Lee, JH, Hong, K, Cho, H, Garg, K, Boggio-Pasqua, M, Rack, JJ, Huse, N, Schoenlein, RW & Kim, TK 2018, 'Transient metal-centered states mediate isomerization of a photochromic ruthenium-sulfoxide complex', Nature communications, vol. 9, no. 1, 1989. https://doi.org/10.1038/s41467-018-04351-0

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

In: Nature communications, Vol. 9, No. 1, 1989, 01.12.2018.

Research output: Contribution to journalArticle

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

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

VL - 9

JO - Nature Communications

JF - Nature Communications

SN - 2041-1723

IS - 1

M1 - 1989

ER -