Elastic Frustration Causing Two-Step and Multistep Transitions in Spin-Crossover Solids: Emergence of Complex Antiferroelastic Structures

TLDR

Two‑step and multistep spin transitions are common in switchable cooperative molecular solids and hold promise for multi‑bit electronics, yet their theory has been limited to phenomenological Ising models despite the recognized central role of elastic interactions driven by volume changes between low‑ and high‑temperature phases. The authors developed the first fully consistent elastic model that incorporates both spin‑induced volume change and elastic frustration to address the shortcomings of previous phenomenological theories. The model reproduces all experimentally observed configurations, showing that varying elastic frustration drives first‑order, gradual, hysteretic two‑step or multistep, and incomplete transitions, and reveals complex antiferro‑elastic patterns in the plateau that explain recent observations of spatially modulated high‑spin fractions.

Abstract

Two-step and multistep spin transitions are frequently observed in switchable cooperative molecular solids. They present the advantage to open the way for three- or several-bit electronics. Despite extensive experimental studies, their theoretical description was to date only phenomenological, based on Ising models including competing ferro- and antiferro-magnetic interactions, even though it is recognized that the elastic interactions are at the heart of the spin transition phenomenon, due to the volume change between the low- and high-temperature phases. To remedy this shortcoming, we designed the first consistent elastic model, taking into account both volume change upon spin transition and elastic frustration. This ingredient was revealed to be powerful, since it was able to obtain all observed experimental configurations in a consistent way. Thus, according to the strength of the elastic frustration, the system may undergo first-order transition with hysteresis, gradual, hysteretic two-step or multistep transitions, and incomplete transitions. Furthermore, the analysis of the spatial organization of the HS and LS species in the plateau regions revealed the emergence of complex antiferro-elastic patterns going from simple antiferro-magnetic-like order to long-range spatial modulations of the high-spin fraction. These results enabled us to identify the elastic frustration as the fundamental mechanism at the origin of the very recent experimental observations showing the existence of organized spatial modulations of the high-spin fraction inside the plateau of two-step spin transitions.