Transferring the entatic-state principle to copper photochemistry
Journal article, 2018
The entatic state denotes a distorted coordination geometry of a complex from its typical arrangement that generates an improvement to its function. The entatic-state principle has been observed to apply to copper electron-transfer proteins and it results in a lowering of the reorganization energy of the electron-transfer process. It is thus crucial for a multitude of biochemical processes, but its importance to photoactive complexes is unexplored. Here we study a copper complex-with a specifically designed constraining ligand geometry-that exhibits metal-to-ligand charge-transfer state lifetimes that are very short. The guanidine-quinoline ligand used here acts on the bis(chelated) copper(I) centre, allowing only small structural changes after photoexcitation that result in very fast structural dynamics. The data were collected using a multimethod approach that featured time-resolved ultraviolet-visible, infrared and X-ray absorption and optical emission spectroscopy. Through supporting density functional calculations, we deliver a detailed picture of the structural dynamics in the picosecond-to-nanosecond time range.
Author
B. Dicke
University of Hamburg
Center for Free-Electron Laser Science (CFEL)
A. Hoffmann
RWTH Aachen University
J. Stanek
RWTH Aachen University
M. S. Rampp
Ludwig Maximilian University of Munich (LMU)
B. Grimm-Lebsanft
University of Hamburg
Center for Free-Electron Laser Science (CFEL)
F. Biebl
Center for Free-Electron Laser Science (CFEL)
University of Hamburg
D. Rukser
Center for Free-Electron Laser Science (CFEL)
University of Hamburg
B. Maerz
Ludwig Maximilian University of Munich (LMU)
D. Goeries
Deutsches Elektronen-Synchrotron (DESY)
M. Naumova
University of Hamburg
Padernborn University
M. Biednov
University of Hamburg
Center for Free-Electron Laser Science (CFEL)
G. Neuber
Center for Free-Electron Laser Science (CFEL)
University of Hamburg
A. Wetzel
University of Hamburg
Center for Free-Electron Laser Science (CFEL)
S. M. Hofmann
Ludwig Maximilian University of Munich (LMU)
P. Roedig
Deutsches Elektronen-Synchrotron (DESY)
A. Meents
Deutsches Elektronen-Synchrotron (DESY)
J. Bielecki
European XFEL
Uppsala University
Jakob Andreasson
Uppsala University
Chalmers, Physics, Condensed Matter Physics
K. R. Beyerlein
Center for Free-Electron Laser Science (CFEL)
H. N. Chapman
Deutsches Elektronen-Synchrotron (DESY)
Center for Free-Electron Laser Science (CFEL)
C. Bressler
European XFEL
Technical University of Denmark (DTU)
University of Hamburg
W. Zinth
Ludwig Maximilian University of Munich (LMU)
M. Ruebhausen
University of Hamburg
Center for Free-Electron Laser Science (CFEL)
S. Herres-Pawlis
RWTH Aachen University
Nature Chemistry
1755-4330 (ISSN) 1755-4349 (eISSN)
Vol. 10 3 355-362Subject Categories
Atom and Molecular Physics and Optics
Other Physics Topics
Theoretical Chemistry
DOI
10.1038/nchem.2916
PubMed
29461525