Transferring the entatic-state principle to copper photochemistry

0501550 - FZÚ 2019 RIV GB eng J - Článek v odborném periodiku
Dicke, B. - Hoffmann, A. - Stanek, J. - Rampp, M.S. - Grimm-Lebsanft, B. - Biebl, F. - Rukser, D. - Maerz, B. - Göries, D. - Naumova, M. - Biednov, M. - Neuber, G. - Wetzel, A. - Hofmann, S.M. - Roedig, P. - Meents, A. - Bielecki, J. - Andreasson, Jakob - Beyerlein, K.R. - Chapman, H.N. - Bressler, C. - Zinth, W. - Rübhausen, M. - Herres-Pawlis, S.
Transferring the entatic-state principle to copper photochemistry.
Nature Chemistry. Roč. 10, č. 3 (2018), s. 355-362. ISSN 1755-4330. E-ISSN 1755-4349
Grant CEP: GA MŠMT EF16_019/0000789; GA MŠMT LQ1606
Grant ostatní: OP VVV - ADONIS(XE) CZ.02.1.01/0.0/0.0/16_019/0000789
Institucionální podpora: RVO:68378271
Klíčová slova: X-ray-absorption spectroscopy * extended X-ray * structural dynamics * electron-transfer * infrared-spectroscopy * fine-structure * coordination-compounds
Obor OECD: Fluids and plasma physics (including surface physics)
Impakt faktor: 23.193, rok: 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.
Trvalý link: http://hdl.handle.net/11104/0293563