Turning graphene magnetic is a promising challenge to make it an active material for spintronics. Predictions state that graphene structures with specific shapes can spontaneously develop magnetism driven by Coulomb repulsion of π-electrons, but its experimental verification is demanding. Here, we report on the observation and manipulation of individual magnetic moments in graphene open-shell nanostructures on a gold surface. Using scanning tunneling spectroscopy, we detect the presence of single electron spins localized around certain zigzag sites of the carbon backbone via the Kondo effect. We find near-by spins coupled into a singlet ground state and quantify their exchange interaction via singlet-triplet inelastic electron excitations. Theoretical simulations picture how electron correlations result in spin-polarized radical states with the experimentally observed spatial distributions. Extra hydrogen atoms bound to radical sites quench their magnetic moment and switch the spin of the nanostructure in half-integer amounts. Our work demonstrates the intrinsic π-paramagnetism of graphene nanostructures.

Mixing of discretized states in quantum magnets has a radical impact on their properties. Managing this effect is key for spintronics in the quantum limit. Magnetic fields can modify state mixing and, for example, mitigate destabilizing effects in single-molecule magnets. The exchange bias field has been proposed as a mechanism for localized control of individual nanomagnets. Here, we demonstrate that exchange coupling with the magnetic tip of a scanning tunnelling microscope provides continuous tuning of spin state mixing in an individual nanomagnet. By directly measuring spin relaxation time with electronic pump-probe spectroscopy, we find that the exchange interaction acts analogously to a local magnetic field that can be applied to a specific atom. It can be tuned in strength by up to several tesla and cancel external magnetic fields, thereby demonstrating the feasibility of complete control over individual quantum magnets with atomically localized exchange coupling.