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 3 355-362

Subject Categories

Atom and Molecular Physics and Optics

Other Physics Topics

Theoretical Chemistry

DOI

10.1038/nchem.2916

PubMed

29461525

More information

Latest update

4/3/2018 1