Ultrafast spectroscopy of the solvent dependence of electron transfer in a perylenebisimide dimer.
We investigate the photoinduced intramolecular electron-transfer (IET) behavior of a perylenebisimide dimer in a variety of solvents using femtosecond transient absorption spectroscopy. Overlapping photoinduced absorptions and stimulated emission give rise to complicated traces, but they are well fit with a simple kinetic model. IET rates were found to depend heavily on solvent dielectric constant. Good quantitative agreement with rates derived from fluorescence quantum yield and time-resolved fluorescence measurements was found for forward electron transfer and charge recombination rates.
Holman
Michael W
MW
Department of Chemistry, Columbia University, New York, New York 10027, USA.
Yan
Ping
P
Adams
David M
DM
Westenhoff
Sebastian
S
Silva
Carlos
C
D000096:Acetone / Q000737:chemistry*; D002725:Chloroform / Q000737:chemistry*; D019281:Dimerization; D004126:Dimethylformamide / Q000737:chemistry*; D004146:Dioxanes / Q000737:chemistry*; D004583:Electrons; D007094:Imides / Q000737:chemistry*; D015394:Molecular Structure; D010569:Perylene / Q000031:analogs & derivatives* / Q000737:chemistry; D010777:Photochemistry; D012680:Sensitivity and Specificity; D012997:Solvents / Q000737:chemistry; D013050:Spectrometry, Fluorescence / Q000379:methods; D013056:Spectrophotometry, Ultraviolet / Q000379:methods
D004146:Dioxanes; D007094:Imides; D012997:Solvents; C510697:perylene bisimide; D000096:Acetone; D010569:Perylene; D002725:Chloroform; D004126:Dimethylformamide; C025223:1,4-dioxane