American Chemical Society
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Electronic and Exchange Coupling in a Cross-Conjugated D–B–A Biradical: Mechanistic Implications for Quantum Interference Effects

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journal contribution
posted on 2016-02-18, 18:54 authored by Martin L. Kirk, David A. Shultz, Daniel E. Stasiw, Diana Habel-Rodriguez, Benjamin Stein, Paul D. Boyle
A combination of variable-temperature EPR spectroscopy, electronic absorption spectroscopy, and magnetic susceptibility measurements have been performed on TpCum,MeZn­(SQ-m-Ph-NN) (1-meta) a donor–bridge–acceptor (D–B–A) biradical that possesses a cross-conjugated meta-phenylene (m-Ph) bridge and a spin singlet ground state. The experimental results have been interpreted in the context of detailed bonding and excited-state computations in order to understand the excited-state electronic structure of 1-meta. The results reveal important excited-state contributions to the ground-state singlet–triplet splitting in this cross-conjugated D–B–A biradical that contribute to our understanding of electronic coupling in cross-conjugated molecules and specifically to quantum interference effects. In contrast to the conjugated isomer, which is a D–B–A biradical possessing a para-phenylene bridge, admixture of a single low-lying singly excited D → A type configuration into the cross-conjugated D–B–A biradical ground state makes a negligible contribution to the ground-state magnetic exchange interaction. Instead, an excited state formed by a Ph-NN (HOMO) → Ph-NN (LUMO) one-electron promotion configurationally mixes into the ground state of the m-Ph bridged D–A biradical. This results in a double (dynamic) spin polarization mechanism as the dominant contributor to ground-state antiferromagnetic exchange coupling between the SQ and NN spins. Thus, the dominant exchange mechanism is one that activates the bridge moiety via the spin polarization of a doubly occupied orbital with phenylene bridge character. This mechanism is important, as it enhances the electronic and magnetic communication in cross-conjugated D–B–A molecules where, in the case of 1-meta, the magnetic exchange in the active electron approximation is expected to be J ∼ 0 cm–1. We hypothesize that similar superexchange mechanisms are common to all cross-conjugated D–B–A triads. Our results are compared to quantum interference effects on electron transfer/transport when cross-conjugated molecules are employed as the bridge or molecular wire component and suggest a mechanism by which electronic coupling (and therefore electron transfer/transport) can be modulated.