Building spin-1/2 antiferromagnetic Heisenberg chains with diaza-nanographenes

Abstract

Understanding and engineering the coupling of spins in nanomaterials is of central importance for designing novel devices. Graphene nanostructures with {\pi}-magnetism offer a chemically tunable platform to explore quantum magnetic interactions. However, realizing spin chains bearing controlled odd-even effects with suitable nanographene systems is challenging. Here, we demonstrate the successful on-surface synthesis of spin-1/2 antiferromagnetic Heisenberg chains with parity-dependent magnetization based on antiaromatic diaza-hexa-peri-hexabenzocoronene (diaza-HBC) units. Using distinct synthetic strategies, two types of spin chains with different terminals were synthesized, both exhibiting a robust odd-even effect on the spin coupling along the chain. Combined investigations using scanning tunneling microscopy, non-contact atomic force microscopy, density functional theory calculations, and quantum spin models confirmed the structures of the diaza-HBC chains and revealed their magnetic properties, which has an S = 1/2 spin per unit through electron donation from the diaza-HBC core to the Au(111) substrate. Gapped excitations were observed in even-numbered chains, while enhanced Kondo resonance emerged in odd-numbered units of odd-numbered chains due to the redistribution of the unpaired spin along the chain. Our findings provide an effective strategy to construct nanographene spin chains and unveil the odd-even effect in their magnetic properties, offering potential applications in nanoscale spintronics.