Covalent Radical Pairs as Spin Qubits: Influence of Rapid Electron Motion between Two Equivalent Sites on Spin Coherence

Ultrafast photodriven electron transfer reactions starting from an excited singlet state in an organic donor–acceptor molecule generate a radical pair (RP) in which the two spins are initially entangled and, in principle, can serve as coupled spin qubits in quantum information science (QIS) applications, provided that spin coherence lifetimes in these RPs are long. Here we investigate the effects of electron transfer between two equivalent sites comprising the reduced acceptor of the RP. A covalent electron donor–acceptor molecule (D–C–A24+) including a p-methoxyaniline donor (D), a 4-aminonaphthalene-1,8-imide chromophoric primary acceptor (C), and a m-xylene bridged cyclophane having two equivalent phenyl-extended viologens (A24+) as a secondary acceptor was synthesized along with the analogous molecule having one phenyl-extended viologen acceptor and a second, more difficult to reduce 2,5-dimethoxyphenyl-extended viologen in a very similar cyclophane structure (D–C–A4+). Photoexcitation of C within each molecule results in subnanosecond formation of D+•–C–A23+• and D+•–C–A3+•. The spin dynamics of these RPs were characterized by time-resolved EPR spectroscopy and magnetic field effects on the RP yield in both CH3CN and CD3CN. The data show that rapid electron hopping within A23+• promotes spin decoherence in D+•–C–A23+• relative to D+•–C–A3+• having a monomeric acceptor, while the interaction of the RP electron spins with the nuclear spins of the solvent have little or no effect on the spin dynamics. These observations provide important information for designing and understanding novel molecular assemblies of spin qubits with long coherence times for QIS applications