Quantum nanomagnets in on-surface metal-free porphyrin chains

Unlike classic spins, quantum magnets are spin systems that interact via the exchange interaction and exhibit collective quantum behaviours, such as fractional excitations. Molecular magnetism often stems from d/f-transition metals, but their spin-orbit coupling and crystal field induce a significant magnetic anisotropy, breaking the rotation symmetry of quantum spins. Thus, it is of great importance to build quantum nanomagnets in metal-free systems. Here we have synthesized individual quantum nanomagnets based on metal-free multi-porphyrin systems. Covalent chains of two to five porphyrins were first prepared on Au(111) under ultrahigh vacuum, and hydrogen atoms were then removed from selected carbons using the tip of a scanning tunnelling microscope. The conversion of specific porphyrin units to their radical or biradical state enabled the tuning of intra- and inter-porphyrin magnetic coupling. Characterization of the collective magnetic properties of the resulting chains showed that the constructed S = 1/2 antiferromagnets display a gapped excitation, whereas the S = 1 antiferromagnets exhibit distinct end states between even- and odd-numbered spin chains, consistent with Heisenberg model calculations.