Zero Quantum Coherence in a Series of Covalent Spin-Correlated Radical Pairs

Photoinitiated subnanosecond electron transfer within covalently linked electron donor–acceptor molecules can result in the formation of a spin-correlated radical pair (SCRP) with a well-defined initial singlet spin configuration. Subsequent coherent mixing between the SCRP singlet and triplet m s = 0 spin states, the so-called zero quantum coherence (ZQC), is of potential interest in quantum information processing applications because the ZQC can be probed using pulse electron paramagnetic resonance (pulse-EPR) techniques. Here, pulse-EPR spectroscopy is utilized to examine the ZQC oscillation frequencies and ZQC dephasing in three structurally well-defined D–A systems. While transitions between the singlet and triplet m s = 0 spin states are formally forbidden (Δ m s = 0), they can be addressed using specific microwave pulse turning angles to map information from the ZQC onto observable single quantum coherences. In addition, by using structural variations to tune the singlet–triplet energy gap, the ZQC frequencies determined for this series of molecules indicate a stronger dependence on the electronic g -factor than on electron–nuclear hyperfine interactions.