A Route toward the On-Surface Synthesis of Organic Ferromagnetic Quantum Spin Chains.

Engineering sublattice imbalance is an intuitive way to induce high-spin ground states in bipartite polycyclic conjugated hydrocarbons (PCHs). Such molecules can be employed as building blocks of quantum spin chains, which are outstanding platforms to study fundamental models in quantum magnetism. This is exemplified by recent reports on the bottom-up synthesis of antiferromagnetic spin chains that provided insights into paradigmatic quantum phenomena such as fractionalization. In contrast to antiferromagnetism, demonstration of ferromagnetic coupling between PCHs has been scarce. Previous attempts in this direction were limited by the formation of nonbenzenoid rings leading to spin quenching or the use of spacer motifs that weaken the magnitude of ferromagnetic exchange. Here, we demonstrate the on-surface synthesis of short ferromagnetic spin chains based on dibenzotriangulene, a triplet PCH. Our synthetic strategy centers on the concept of achieving a direct (without spacer motifs) majority-minority sublattice coupling between adjacent molecules. This leads to a global sublattice imbalance in spin chains scaling with the chain length and therefore a ferromagnetic ground state with a strong intermolecular ferromagnetic exchange. Through scanning probe measurements and quantum chemical calculations, we analyze the electronic and magnetic properties of ferromagnetic dimers and trimers of dibenzotriangulene and confirm their quintet and septet ground states, respectively, with an intermolecular ferromagnetic exchange of 7 meV. Furthermore, we elucidate the role of sublattice coupling on magnetism through complementary experiments on antiferromagnetic dibenzotriangulene dimers with majority-majority and minority-minority sublattice couplings. We expect our study to provide impetus for the design of organic ferromagnetic materials.