Polymer Mediated Control and Migration Effects in Spin-Crossover-Polymer Hybrids Towards Tunable Thermal Sensing Applications

Tailoring the spin crossover (SCO) effect in molecular materials remains a fundamental challenge, driven by the need to control critical parameters, such as the spin transition temperature (T₁/₂), hysteresis width, cooperativity, and switching kinetics for applications in sensing, memory, and actuation devices. SCO behavior is highly sensitive to small changes in the structure or crystal structure of the surrounding environment. In this context, achieving predictable and reproducible control remains elusive. Embedding SCO complexes into polymer matrices offers a more versatile and processable approach, but understanding how matrix–guest interactions affect spin-state behavior is still limited. In this study, we investigate a polymer-mediated strategy to tune SCO properties by incorporating the well-characterized Fe(II) complex [Fe(1,10-phenanthroline)₂(NCS)₂] into three polymers with distinct structural features: polylactic acid (PLA), polystyrene (PS), and polysulfone (PSF). In terms of potential electrostatic interaction between the complex and the polymeric matrixes, the polymers offer distinct features. Either there does not seem to be any specific interaction (PLA case) or, rather, there is π-π stacking between the aromatic rings of the SCO complex, and the corresponding ones present either in the backbone or in the side chain of the polymer (PSF and PS, respectively). The latter can potentially influence spin-state energetics and dynamics. Importantly, we also reveal and quantify the migration behavior of SCO particles within different polymer matrices, an aspect that has not been previously examined in SCO–polymer systems. Using magnetic susceptibility, spectroscopic, diffraction, and migration studies, we show that the polymer environment, PLA as well, actively modulates the SCO response. PSF yields lower T₁/₂, slower switching kinetics, and enhanced retention of the complex, indicative of strong matrix confinement and interaction. In contrast, PLA and PS composites exhibit sharper transitions and higher migration, suggesting weaker interactions and greater mobility. In addition, the semi-crystalline nature of PLA seems to induce the extension of the hysteresis width. These results highlight both the challenge and the opportunity in SCO polymer composites to tune SCO behavior, offering a scalable route toward functional hybrid materials for thermal sensing and responsive devices.