Dynamics of ultrafast intramolecular charge transfer with 4-(dimethylamino)benzonitrile in acetonitrile

The Journal of Physical Chemistry. a
Sergey I DruzhininKlaas A Zachariasse

Abstract

The kinetics of the intramolecular charge-transfer (ICT) reaction of 4-(dimethylamino)benzonitrile (DMABN) in the polar solvent acetonitrile (MeCN) is investigated by fluorescence quantum yield and picosecond time-correlated single photon counting (SPC) experiments over the temperature range from -45 to +75 degrees C, together with femtosecond Sn <-- S1 transient absorption measurements at room temperature. For DMABN in MeCN, the fluorescence from the locally excited (LE) state is strongly quenched, with an unquenched to quenched fluorescence quantum yield ratio of 290 at 25 degrees C. Under these conditions, even very small amounts of the photoproduct 4-(methylamino)benzonitrile (MABN) severely interfere, as the LE fluorescence of MABN is in the same spectral range as that of DMABN. The influence of photoproduct formation could be overcome by a simultaneous analysis of the picosecond and photostationary measurements, resulting in data for the activation barriers Ea (5 kJ/mol) and Ed (32 kJ/mol) of the forward and backward ICT reaction as well as the ICT reaction enthalpy and entropy: DeltaH (-27 kJ/mol) and DeltaS [-38 J/(mol K)]. The reaction hence takes place over a barrier, with double-exponential fluorescence decays, as to...Continue Reading

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Citations

Jun 16, 2012·Chemical Reviews·N Mariano CorreaNancy E Levinger
Aug 10, 2011·The Journal of Chemical Physics·Raúl MonteroAsier Longarte
Apr 20, 2017·Physical Chemistry Chemical Physics : PCCP·Malgorzata BaydaBronislaw Marciniak
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