Two different mechanisms of stabilization of regular pi-stacks of radicals in switchable dithiazolyl-based materialsFrancese, T., Vela, S., Deumal, M., Mota, F., Novoa, J. J., Camellone, M. F., Fabris, S., Havenith, R. W. A., Broer, R. & Ribas-Arino, J., 28-Apr-2020, In : Journal of Materials Chemistry C. 8, 16, p. 5437-5448 12 p.
Research output: Contribution to journal › Article › Academic › peer-review
Materials based on regular pi-stacks of planar organic radicals are intensively pursued by virtue of their technologically relevant properties. Yet, these pi-stacks are commonly unstable against pi-dimerization. In this computational study, we reveal that regular pi-stacks of planar dithiazolyl radicals can be rendered stable, in some range of temperatures,viatwo different mechanisms. When the radicals of a pi-stack are both longitudinally and latitudinally slipped with respect to each other, the corresponding regular pi-stacked configuration is associated with a locally stable minimum in the potential energy surface of the system. Conversely, those regular pi-stacks in which radicals are latitudinally slipped with respect to each other are stable as a result of a dynamic interconversion between two degenerate dimerized configurations. The existence of two stabilization mechanisms, which can be traced back to the bonding properties of isolated pi-dimers, translates into two different ways of exploiting spin-Peierls-like transitions in switchable dithiazolyl-based materials.
|Number of pages||12|
|Journal||Journal of Materials Chemistry C|
|Publication status||Published - 28-Apr-2020|
- MAGNETIC-PROPERTIES, BISDITHIAZOLYL RADICALS, MOLECULAR MATERIALS, SPIN TRANSITIONS, BASIS-SETS, BISTABILITY, PSEUDOPOTENTIALS, EXCHANGE, VALENCE, LONG