Spin-Crossover Complexes in Nanoscale Devices: Main Ingredients of the Molecule-Substrate Interactions

Spin-crossover complexes embedded in nanodevices experience effects that are absent in the bulk that can modulate, quench and even suppress the spin-transition. In this work we explore, by means of state-of-the-art quantum chemistry calculations, different aspects of the integration of SCO molecules on active nanodevices, such as the geometry and energetics of the interaction with the substrate, extension of the charge transfer between the substrate and SCO molecule, impact of the applied external electric field on the spin-transition, and sensitivity of the transport properties on the local conditions of the substrate. We focus on the recently reported encapsulation of Fe(ii) spin-crossover complexes in single-walled carbon nanotubes, with new measurements that support the theoretical findings. Even so our results could be useful to many other systems where SCO phenomena take place at the nanoscale, the spin-state switching is probed by an external electric field or current, or the substrate is responsible for the quenching of the SCO mechanism. © 2021 The Royal Society of Chemistry.