Dynamical effects on the magnetic properties of dithiazolyl bistable materials

The magnetic properties of molecule-based magnets are commonly rationalized by considering only a single nuclear configuration of the system under study (usually an X-ray crystal structure). Here, by means of a computational study, we compare the results obtained using such a static approach with those obtained by explicitly accounting for thermal fluctuations, and uncover the serious limitations of the static perspective when dealing with magnetic crystals whose radicals undergo wide-amplitude motions. As a proof of concept, these limitations are illustrated for the magnetically bistable 1,3,5-trithia-2,4,6-triazapentalenyl (TTTA) material. For its high-temperature phase at 300 K, we show that nuclear dynamics induce large fluctuations in the magnetic exchange interactions (J (AB)) between spins (up to 1000% of the average value). These deviations result in a ∼20% difference between the 300 K magnetic susceptibility computed by explicitly considering the nuclear dynamics and that computed using the X-ray structure, the former being in better agreement with the experimental data. The unveiled strong coupling between J (AB) interactions and intermolecular vibrations reveals that considering J (AB) as a constant value at a given temperature (as always done in molecular magnetism) leads to a flawed description of the magnetism of TTTA. Instead, the physically relevant concept in this case is the statistical distribution of J (AB) values. The discovery that a single X-ray structure is not adequate enough to interpret the magnetic properties of TTTA is also expected to be decisive in other organic magnets with dominant exchange interactions propagating through labile π–π networks.