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Excited state intramolecular charge transfer reaction of 4-(morpholenyl) benzonitrile in solution: Effects of hetero atom in the donor moiety

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Abstract

An intramolecular charge transfer (ICT) molecule with an extra hetero atom in its donor moiety has been synthesized in order to investigate how ICT reaction is affected by hetero atom replacement. Photo-physical and photo-dynamical properties of this molecule, 4-(morpholenyl)benzonitrile (M6C), have been studied in 20 different solvents. The correlation between the reaction driving force (−ΔG r ) and activation barrier (ΔG #) has been explored in order to understand the solvent effects (static and dynamic) on the photo-excited ICT reaction in this molecule. A Kramer’s model analysis of the experimentally observed reaction rate constants indicates a solvent-averaged activation barrier of ∼4 k B T in the absence of solvent dynamical control. The reaction in M6C is therefore not a barrier-less reaction but close to the limit where conventional kinetics might break down.

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Authors and Affiliations

  1. Department of Chemical, Biological and Macromolecular Sciences, S.N. Bose National Centre for Basic Sciences, J.D. Block, Sector III, Salt Lake, Kolkata, 700 098, India

    Tuhin Pradhan, Harun Al Rasid Gazi & Ranjit Biswas

Authors
  1. Tuhin Pradhan
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  2. Harun Al Rasid Gazi
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  3. Ranjit Biswas
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Correspondence to Ranjit Biswas.

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Pradhan, T., Gazi, H.A.R. & Biswas, R. Excited state intramolecular charge transfer reaction of 4-(morpholenyl) benzonitrile in solution: Effects of hetero atom in the donor moiety. J Chem Sci 122, 481–490 (2010). https://doi.org/10.1007/s12039-010-0083-y

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  • DOI: https://doi.org/10.1007/s12039-010-0083-y

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