Coupled spin-crossover complexes in supramolecular systems feature rich spin phases that can exhibit collective behaviors. Here, we report on a molecular-level exploration of the spin phase and collective spin-crossover dynamics in metallo-supramolecular chains. Using scanning tunneling microscopy, spectroscopy, and density functional theory calculations, we identify an antiferroelastic phase in the metal-organic chains, where the Ni atoms coordinated by deprotonated tetrahydroxybenzene linkers on Au(111) are at a low-spin (S = 0) or a high-spin (S = 1) state alternately along the chains. We demonstrate that the spin phase is stabilized by the combined effects of intrachain interactions and substrate commensurability. The stability of the antiferroelastic structure drives the collective spin-state switching of multiple Ni atoms in the same chain in response to electron/hole tunneling to a Ni atom via a domino-like magnetostructural relaxation process. These results provide insights into the magnetostructural dynamics of the supramolecular structures, offering a route toward their spintronic manipulations.
Keywords: antiferroelastic phases; collective spin-state switching; density functional theory; metallo-supramolecular chains; scanning tunneling microscopy; scanning tunneling spectroscopy; spin-crossover.