Home Estimation of the Fraction of Spin-Correlated Radical Ion Pairs in Irradiated Alkanes using Magnetosensitive Recombination Luminescence from Exciplexes Generated upon Recombination of a Probe Pair
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Estimation of the Fraction of Spin-Correlated Radical Ion Pairs in Irradiated Alkanes using Magnetosensitive Recombination Luminescence from Exciplexes Generated upon Recombination of a Probe Pair

  • Anatoly R. Melnikov EMAIL logo , Vladimir N. Verkhovlyuk , Evgeny V. Kalneus , Valeri V. Korolev , Vsevolod I. Borovkov , Peter S. Sherin , Maria P. Davydova , Sergei F. Vasilevsky and Dmitri V. Stass
Published/Copyright: September 28, 2016
Zeitschrift für Physikalische Chemie
From the journal Zeitschrift für Physikalische Chemie Volume 231 Issue 2

Abstract

We suggest a convenient probe exciplex system for studies in radiation spin chemistry based on a novel acceptor-substituted diphenylacetylene, 1-(phenylethynyl)-4-(trifluoromethyl)benzene that has a very short fluorescence lifetime (<200 ps) and low quantum yield (0.01) of intrinsic emission, provides efficient electron capture in alkanes and efficient exciplex formation upon recombination in pair with DMA radical cation, while exhibiting a shifted to red exciplex emission band as compared to the parent system DMA – diphenylacetylene. After chemical, luminescent, radiation and spin-chemical characterization of the new system we used the magnitude of magnetic field effect in its exciplex emission band for experimental estimation of the fraction of spin-correlated radical ion pairs under X-irradiation with upper energy cutoff 40 keV in a set of 11 alkanes. For linear and branched alkanes magnetic field effects and the corresponding fractions are approximately 19–20% and 0.28, while for cyclic alkanes they are lower at 16–17% and 0.22, respectively.

Keywords: diphenylacetylene; exciplex luminescence; magnetic field effect; radical ion pair; spin correlation; X-ray irradiation

Dedicated to: Kev Salikhov on the occasion of his 80th birthday.

Acknowledgments

The work was supported by Russian Science Foundation (project no. 16-13-10163). A.R.M. is grateful to the Council for Grants of the President of the Russian Federation for awarding a personal scholarship for Support of Young Researchers (project no. SP-81.2016.1).

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Supplemental Material:

The online version of this article (DOI: 10.1515/zpch-2016-0819) offers supplementary material, available to authorized users.

Received: 2016-6-14
Accepted: 2016-8-26
Published Online: 2016-9-28
Published in Print: 2017-2-1

©2017 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Preface
  3. Editorial Review
  4. From Free Radicals and Spin-Chemistry Over Spin-Dynamics and Hyperpolarization to Biology and Materials Science
  5. On Relations Between Singlet and Triplet Recombination Yields for Singlet and Triplet Precursors
  6. The Quantum Dynamical Basis of a Classical Kinetic Scheme Describing Coherent and Incoherent Regimes of Radical Pair Recombination
  7. Reaction Operators for Radical Pairs. The Exactly Solvable Model
  8. Estimation of the Fraction of Spin-Correlated Radical Ion Pairs in Irradiated Alkanes using Magnetosensitive Recombination Luminescence from Exciplexes Generated upon Recombination of a Probe Pair
  9. Theoretical Description of Pulsed RYDMR: Refocusing Zero-Quantum and Single Quantum Coherences
  10. A Transient EPR Study of Electron Transfer in Tetrathiafulvalene-Aluminum(III) Porphyrin-Anthraquinone Supramolecular Triads
  11. Solvent Radical Anions in Irradiated Aliphatic Ketones and Esters as Observed Using Time-Resolved Magnetic Field Effects in the Recombination Fluorescence
  12. Effect of Dehydrated Trehalose Matrix on the Kinetics of Forward Electron Transfer Reactions in Photosystem I
  13. Photo-CIDNP in the Reaction Center of the Diatom Cyclotella meneghiniana Observed by 13C MAS NMR
  14. Light-Stimulated Generation of Free Radicals by Quinones-Chelators
  15. Influence of C2-Methylation of Imidazolium Based Ionic Liquids on Photoinduced Spin Dynamics of the Dissolved ZnTPP Studied by Time-Resolved EPR
  16. ESR Study of Electron States in Ge/Si Heterostructures with Nanodisc Shaped Quantum Dots
  17. Novel Anthrathiophene-Based Small Molecules as Donor Material for Organic Photovoltaics: Synthesis and Light-Induced EPR Study
  18. Structural Determination of a DNA Oligomer for a Molecular Spin Qubit Lloyd Model of Quantum Computers
https://doi.org/10.1515/zpch-2016-0819
Keywords for this article
diphenylacetylene; exciplex luminescence; magnetic field effect; radical ion pair; spin correlation; X-ray irradiation

Articles in the same Issue

  1. Frontmatter
  2. Preface
  3. Editorial Review
  4. From Free Radicals and Spin-Chemistry Over Spin-Dynamics and Hyperpolarization to Biology and Materials Science
  5. On Relations Between Singlet and Triplet Recombination Yields for Singlet and Triplet Precursors
  6. The Quantum Dynamical Basis of a Classical Kinetic Scheme Describing Coherent and Incoherent Regimes of Radical Pair Recombination
  7. Reaction Operators for Radical Pairs. The Exactly Solvable Model
  8. Estimation of the Fraction of Spin-Correlated Radical Ion Pairs in Irradiated Alkanes using Magnetosensitive Recombination Luminescence from Exciplexes Generated upon Recombination of a Probe Pair
  9. Theoretical Description of Pulsed RYDMR: Refocusing Zero-Quantum and Single Quantum Coherences
  10. A Transient EPR Study of Electron Transfer in Tetrathiafulvalene-Aluminum(III) Porphyrin-Anthraquinone Supramolecular Triads
  11. Solvent Radical Anions in Irradiated Aliphatic Ketones and Esters as Observed Using Time-Resolved Magnetic Field Effects in the Recombination Fluorescence
  12. Effect of Dehydrated Trehalose Matrix on the Kinetics of Forward Electron Transfer Reactions in Photosystem I
  13. Photo-CIDNP in the Reaction Center of the Diatom Cyclotella meneghiniana Observed by 13C MAS NMR
  14. Light-Stimulated Generation of Free Radicals by Quinones-Chelators
  15. Influence of C2-Methylation of Imidazolium Based Ionic Liquids on Photoinduced Spin Dynamics of the Dissolved ZnTPP Studied by Time-Resolved EPR
  16. ESR Study of Electron States in Ge/Si Heterostructures with Nanodisc Shaped Quantum Dots
  17. Novel Anthrathiophene-Based Small Molecules as Donor Material for Organic Photovoltaics: Synthesis and Light-Induced EPR Study
  18. Structural Determination of a DNA Oligomer for a Molecular Spin Qubit Lloyd Model of Quantum Computers
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