Strong Modulation of the Exchange Interaction in a Spin-Polarized, Aryl 
Ether-Linked 1,14-Biradical

Avdievich, NI; Forbes, MDE

doi:10.1021/jp9531422

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Strong Modulation of the Exchange Interaction in a Spin-Polarized, Aryl Ether-Linked 1,14-Biradical

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https://pubs.acs.org/doi/pdf/10.1021/jp9531422
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Avdievich, N., & Forbes, M. (1996). Strong Modulation of the Exchange Interaction in a Spin-Polarized, Aryl Ether-Linked 1,14-Biradical. The Journal of Physical Chemistry, 100(6), 1993-1995. doi:10.1021/jp9531422.

Cite as: https://hdl.handle.net/21.11116/0000-0005-E93E-0

Abstract

The time-resolved electron paramagnetic resonance spectrum of a 1,14-bis(alkyl)biradical linked via the para position of an aryl ether moiety has been studied. Previously the spectrum obtained at 50 °C could not be simulated using spin-correlated radical pair (SCRP) theory. It is successfully simulated here by adding modulation of the exchange interaction (J) to the fitting routine as a T2 relaxation mechanism. Inclusion of this line-broadening effect allowed an accurate value of the exchange interaction to be determined for this temperature. Comparison of this J value with that obtained in previous work for the meta isomer of the same biradical showed that the dominant mechanism of J coupling is through-solvent rather than through-bond. The magnitude of the J modulation matrix elements in the two isomers are discussed as are their temperature dependencies.