Geometry changes of a Cu(I) phenanthroline complex on photoexcitation in a confining medium by time-resolved X-ray diffraction.
Using a stroboscopic technique, in which the molecule is repeatedly excited and the structural change is probed more than 5000 times per second immediately after excitation, we performed a 16 K time-resolved single-crystal study of the microsecond lifetime triplet state of the Cu(I)phenanthroline derivative[Cu(I)(dmp)(dppe)][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane). The geometry changes on excitation differ for the two symmetry-independent molecules, but are in the same direction as calculated for an isolated reference molecule, although the flattening distortion in the crystal is significantly smaller, implying that the reorganization energy is greatly affected by the confining medium.
Coppens
Philip
P
Department of Chemistry, State University of New York at Buffalo, Buffalo, New York 14260, USA. coppens@buffalo.edu
Vorontsov
Ivan I
II
Graber
Timothy
T
Kovalevsky
Andrey Yu
AY
Chen
Yu-Sheng
YS
Wu
Guang
G
Gembicky
Milan
M
Novozhilova
Irina V
IV