| Literature DB >> 29461525 |
B Dicke1,2, A Hoffmann3, J Stanek3, M S Rampp4, B Grimm-Lebsanft1,2, F Biebl1,2, D Rukser1,2, B Maerz4, D Göries5, M Naumova1,6, M Biednov1,2, G Neuber1,2, A Wetzel1,2, S M Hofmann4, P Roedig5, A Meents5, J Bielecki7,8, J Andreasson7,9,10, K R Beyerlein2, H N Chapman2,5, C Bressler8,11,12, W Zinth4, M Rübhausen1,2, S Herres-Pawlis3.
Abstract
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.Entities:
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Year: 2018 PMID： 29461525 DOI： 10.1038/nchem.2916
Source DB: PubMed Journal: Nat Chem ISSN： 1755-4330 Impact factor: 24.427