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What Determines the Rate of Excited‐State Intramolecular Electron‐Transfer Reaction of 4‐( N , N ′‐dimethylamino)benzonitrile in Room Temperature Ionic Liquids? A Study in [bmim][PF 6 ]
Author(s) -
Santhosh Kotni,
Samanta Anunay
Publication year - 2012
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201100655
Subject(s) - chemistry , excited state , solvation , intramolecular force , benzonitrile , electron transfer , photochemistry , picosecond , relaxation (psychology) , molecule , atomic physics , stereochemistry , organic chemistry , psychology , social psychology , laser , physics , optics
The kinetics of excited‐state intramolecular electron‐transfer reaction and dynamics of solvation of the intramolecular charge transfer (ICT) state of 4‐( N , N ′‐dimethylamino)benzonitrile (DMABN) was studied in 1‐butyl‐3‐methylimidazloium hexafluorophosphate, [bmim][PF 6 ], by monitoring the dual fluorescence of the system. The picosecond time‐resolved emission spectra (TRES) of DMABN exhibit decay of the locally excited (LE) emission intensity and shift of the ICT emission peak position with time, thus capturing the kinetics of evolution of the ICT state from the LE state and solvent relaxation of the ICT state. These results show that the LE→ICT transformation rate is determined not by the slow dynamics of solvation in ionic liquid, but is controlled mainly by the rate of structural reorganization of the molecule, which accompanies the electron‐transfer process in this polar viscous medium. Even though both solvent reorganization around photo‐excited DMABN and structural rearrangement of the molecule are dependent on the viscosity of the medium, it is the latter process that contributes to the viscosity dependence of the LE→ICT transformation.