Regulation of quantum spin conversions in a single molecular radical

Free radicals, generally formed through the cleavage of covalent electron-pair bonds, play an important role in diverse fields ranging from synthetic chemistry to spintronics and nonlinear optics. However, the characterization and regulation of the radical state at a single-molecule level face formidable challenges. Here we present the detection and sophisticated tuning of the open-shell character of individual diradicals with a donor-acceptor structure via a sensitive single-molecule electrical approach. The radical is sandwiched between nanogapped graphene electrodes via covalent amide bonds to construct stable graphene-molecule-graphene single-molecule junctions. We measure the electrical conductance as a function of temperature and track the evolution of the closed-shell and open-shell electronic structures in real time, the open-shell triplet state being stabilized with increasing temperature. Furthermore, we tune the spin states by external stimuli, such as electrical and magnetic fields, and extract thermodynamic and kinetic parameters of the transition between closed-shell and open-shell states. Our findings provide insights into the evolution of single-molecule radicals under external stimuli, which may proof instrumental for the development of functional quantum spin-based molecular devices.