Modulating unimolecular charge transfer by exciting bridge vibrations.
Ultrafast UV-vibrational spectroscopy was used to investigate how vibrational excitation of the bridge changes photoinduced electron transfer between donor (dimethylaniline) and acceptor (anthracene) moieties bridged by a guanosine-cytidine base pair (GC). The charge-separated (CS) state yield is found to be lowered by high-frequency bridge mode excitation. The effect is linked to a dynamic modulation of the donor-acceptor coupling interaction by weakening of H-bonding and/or by disruption of the bridging base-pair planarity.
Lin
Zhiwei
Z
Department of Chemistry, Tulane University, New Orleans, Louisiana 70118, USA.
Lawrence
Candace M
CM
Xiao
Dequan
D
Kireev
Victor V
VV
Skourtis
Spiros S
SS
Sessler
Jonathan L
JL
Beratan
David N
DN
Rubtsov
Igor V
IV
D000814:Aniline Compounds / Q000737:chemistry* / Q000528:radiation effects; D000873:Anthracenes / Q000737:chemistry* / Q000528:radiation effects; D003562:Cytidine / Q000737:chemistry / Q000528:radiation effects; D004579:Electron Transport; D006151:Guanosine / Q000737:chemistry / Q000528:radiation effects; D006860:Hydrogen Bonding; D007700:Kinetics; D008956:Models, Chemical; D015394:Molecular Structure; D010777:Photochemistry; D013056:Spectrophotometry, Ultraviolet; D014732:Vibration
D000814:Aniline Compounds; D000873:Anthracenes; D006151:Guanosine; D003562:Cytidine; C015157:N,N-dimethylaniline; C034020:anthracene