000001535 001__ 1535
000001535 005__ 20190130104944.0
000001535 02470 $$2doi$$a10.1038/nchem.2916
000001535 037__ $$aARTICLE-2018-028
000001535 041__ $$aeng
000001535 245__ $$aTransferring the entatic-state principle to copper photochemistry
000001535 260__ $$aLondon$$bNature Publishing Group$$c2018$$hUK
000001535 269__ $$a2018
000001535 336__ $$aArticles
000001535 520__ $$aThe 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.
000001535 546__ $$aEnglish
000001535 655__ $$aFemtochemistry and solid- and liquid-state chemistry
000001535 690__ $$aExternal experiment
000001535 7001_ $$01188$$aDicke, B.
000001535 7001_ $$aHoffmann, A.
000001535 7001_ $$aStanek, J.
000001535 7001_ $$aRampp, M. S.
000001535 7001_ $$aGrimm-Lebsanft, B.
000001535 7001_ $$aBiebl, F.
000001535 7001_ $$aRukser, D.
000001535 7001_ $$aMaerz, B.
000001535 7001_ $$01308$$aGöries, D.
000001535 7001_ $$aNaumova, M.
000001535 7001_ $$01645$$aBiednov, M.
000001535 7001_ $$aNeuber, G.
000001535 7001_ $$aWetzel, A.
000001535 7001_ $$aHofmann, S. M.
000001535 7001_ $$aRoedig, P.
000001535 7001_ $$aMeents, A.
000001535 7001_ $$01624$$aBielecki, J.
000001535 7001_ $$aAndreasson, J.
000001535 7001_ $$aBeyerlein, K. R.
000001535 7001_ $$aChapman, H. N.
000001535 7001_ $$01111$$aBressler, C.
000001535 7001_ $$aZinth, W.
000001535 7001_ $$aRübhausen, M.
000001535 7001_ $$aHerres-Pawlis, S.
000001535 770__ $$x1755-4349
000001535 773__ $$j10$$pNat. Chem.$$q355–362$$tNature Chemistry
000001535 790__ $$aEuXFEL staff
000001535 790__ $$aOther
000001535 85641 $$uhttps://www.nature.com/articles/nchem.2916
000001535 8560_ $$fkurt.ament@xfel.eu
000001535 900__ $$aInstrument FXE
000001535 980__ $$aARTICLE