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Formation of cation–radical anion pairs derived from carboxybenzophenone–tetrabutylammonium salts. Pulse radiolysis studies

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Abstract

Pulse radiolysis of acetonitrile solutions of tetra-n-butyl ammonium salts of 2- and 4-carboxybenzophenones [BP-COO−···N+(C4H9)4] were performed in order to generate directly the reduced forms of the benzophenone moieties within pre-formed ion pairs. In earlier studies on photochemical electron transfer reactions, ion pairs containing a tetraalkyl ammonium cation and a benzophenone radical anion were formed in an electron transfer to the triplet BP from a quencher consisting of a tetraalkyl ammonium salt of (phenylthio)acetic acid. In the current work, the [BP•−COO−···N+(C4H9)4] ion pairs were formed by direct reduction of the salts without the complication of a third moiety, i.e., the (phenylthio)acetic anion. The spectra and kinetic parameters of the radiolytically-reduced salts were compared to the behavior of reduced forms of the 2- and 4-COOH substituted benzophenones. The results from the pulse radiolysis and photochemistry were compared and explained in terms of the different structures of the ion pairs.

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Acknowledgments

This work described herein was supported by the Ministry of Research and Higher Education Poland (Grant No. 3 T09A 165 28). This is Document No. NDRL 4784 from the Notre Dame Radiation Laboratory. The Notre Dame Radiation Laboratory is supported by the Office of Basic Energy Sciences of the U.S. Department of Energy.

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Authors and Affiliations

  1. Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780, Poznan, Poland

    Piotr Filipiak, Gordon L. Hug & Bronislaw Marciniak

  2. Radiation Laboratory, University of Notre Dame, Notre Dame, IN, 46556, USA

    Gordon L. Hug

  3. Scientific Department – The Centre of Radiation Research and Technology, Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195, Warsaw, Poland

    Krzysztof Bobrowski

  4. Faculty of Chemical Technology, University of Technology and Life Sciences, 85-326, Bydgoszcz, Poland

    Marek Pietrzak & Jerzy Paczkowski

Authors
  1. Piotr Filipiak
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  2. Gordon L. Hug
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  3. Krzysztof Bobrowski
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  4. Marek Pietrzak
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  5. Jerzy Paczkowski
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  6. Bronislaw Marciniak
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Correspondence to Bronislaw Marciniak.

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Filipiak, P., Hug, G.L., Bobrowski, K. et al. Formation of cation–radical anion pairs derived from carboxybenzophenone–tetrabutylammonium salts. Pulse radiolysis studies. Res Chem Intermed 35, 389–399 (2009). https://doi.org/10.1007/s11164-009-0050-8

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