Photoionization of TMPD in DMSO solution: mechanism and magnetic field effects

K. B. Henbest Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, Oxford, OX1 3QR, UK; Department of Chemistry, University of Oxford, Physical and Theoretical Chemistry Laboratory, Oxford, OX1 3QZ, UK

E. Athanassiades Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, Oxford, OX1 3QR, UK; Department of Chemistry, University of Oxford, Physical and Theoretical Chemistry Laboratory, Oxford, OX1 3QZ, UK

K. Maeda Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, Oxford, OX1 3QR, UK; Department of Chemistry, University of Oxford, Physical and Theoretical Chemistry Laboratory, Oxford, OX1 3QZ, UK

I. Kuprov Department of Chemistry, University of Oxford, Physical and Theoretical Chemistry Laboratory, Oxford, OX1 3QZ, UK

P. J. Hore Department of Chemistry, University of Oxford, Physical and Theoretical Chemistry Laboratory, Oxford, OX1 3QZ, UKCorrespondence[email protected]

C. R. Timmel Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, Oxford, OX1 3QR, UK; Department of Chemistry, University of Oxford, Physical and Theoretical Chemistry Laboratory, Oxford, OX1 3QZ, UKCorrespondence[email protected]

Abstract

Photoionization of N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD) in alcoholic solution produces the radical ion pair [TMPD^•+ e⁻]. However, the identity of the negatively charged counter-radical formed by photolysis of TMPD in DMSO (dimethylsulphoxide)/toluene mixtures, for which unusually large effects of weak applied magnetic fields have been observed, is unclear. Modulated MARY (Magnetically Affected Reaction Yield) experiments on solutions containing different isotopomers of TMPD, DMSO and toluene show that the counter-radical is likely to be the solvated electron. This result supports the idea that large effects of weak fields on radical recombination yields can be expected for radical pairs in which the electron–nuclear hyperfine interactions are concentrated in one of the radicals, rather than being distributed more evenly between the two radicals.

Acknowledgements

We thank the EPSRC, the Human Frontier Science Programme and the EMF Biological Research Trust for financial support. CRT is grateful for a Royal Society University Research Fellowship. We gratefully acknowledge support from the Oxford Supercomputing Centre.

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Photoionization of TMPD in DMSO solution: mechanism and magnetic field effects

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Photoionization of TMPD in DMSO solution: mechanism and magnetic field effects

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