Transferring the entatic-state principle to copper photochemistry
Artikel i vetenskaplig tidskrift, 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.
Författare
B. Dicke
Universität Hamburg
Center for Free-Electron Laser Science (CFEL)
A. Hoffmann
RWTH Aachen University
J. Stanek
RWTH Aachen University
M. S. Rampp
Ludwig-Maximilians-Universität München (LMU)
B. Grimm-Lebsanft
Universität Hamburg
Center for Free-Electron Laser Science (CFEL)
F. Biebl
Center for Free-Electron Laser Science (CFEL)
Universität Hamburg
D. Rukser
Center for Free-Electron Laser Science (CFEL)
Universität Hamburg
B. Maerz
Ludwig-Maximilians-Universität München (LMU)
D. Goeries
Deutsches Elektronen-Synchrotron (DESY)
M. Naumova
Universität Hamburg
Universität Paderborn
M. Biednov
Universität Hamburg
Center for Free-Electron Laser Science (CFEL)
G. Neuber
Center for Free-Electron Laser Science (CFEL)
Universität Hamburg
A. Wetzel
Universität Hamburg
Center for Free-Electron Laser Science (CFEL)
S. M. Hofmann
Ludwig-Maximilians-Universität München (LMU)
P. Roedig
Deutsches Elektronen-Synchrotron (DESY)
A. Meents
Deutsches Elektronen-Synchrotron (DESY)
J. Bielecki
European XFEL
Uppsala universitet
Jakob Andreasson
Uppsala universitet
Chalmers, Fysik, Kondenserade materiens fysik
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
Danmarks Tekniske Universitet (DTU)
Universität Hamburg
W. Zinth
Ludwig-Maximilians-Universität München (LMU)
M. Ruebhausen
Universität Hamburg
Center for Free-Electron Laser Science (CFEL)
S. Herres-Pawlis
RWTH Aachen University
Nature Chemistry
1755-4330 (ISSN) 1755-4349 (eISSN)
Vol. 10 3 355-362Ämneskategorier
Atom- och molekylfysik och optik
Annan fysik
Teoretisk kemi
DOI
10.1038/nchem.2916
PubMed
29461525