Magnetic field effects in rigidly linked D-A dyads: Extreme on-resonance quantum coherence effect on charge...

Charge recombination in the photoinduced charge separated (CS) state of a rigidly linked donor/bridge/acceptor triad with a triarylamine (TAA) donor, a 1,3-diethynyl-2,5-dimethoxy benzene bridge (OMe), and a perylenediimide (PDI) unit as an acceptor, represents a spin chemical paradigm case of a rigid radical ion pair formed with singlet spin and recombining almost exclusively to the locally excited PDI triplet state (³PDI). The magnetic field dependence of the CS state decay and ³PDI formation kinetics are investigated from 0 to 1800 mT by nanosecond laser flash spectroscopy. The time-resolved magnetic field affected reaction yields spectra of the CS state population and ³PDI population exhibit a sharp and deep resonance at 18.9 mT, indicating level crossing of the S and T₊ levels separated by an exchange interaction of J = 18.9/2 mT at zero field. The kinetics are biexponential around the resonance field and monoexponential outside that range. The monoexponential behavior can be simulated by a classical kinetic model assuming a single field dependent double Lorentzian function for the energy gap dependence of all spin conversion processes. The full field dependence of the kinetics has been simulated quantum theoretically. It has been shown that incoherent and coherent hyperfine coupling contribute to S/T₊ spin conversion at all fields and that the biexponentiality of the kinetics at resonance is due to a partitioning of the overall kinetics into 2/3 of the singlet hyperfine states exhibiting strong isotropic coupling to T₊ and 1/3 of the singlet hyperfine states that do not or only weakly couple isotropically to T₊.