Two different mechanisms of stabilization of regular pi-stacks of radicals in switchable dithiazolyl-based materials

Tommaso Francese, Sergi Vela, Merce Deumal, Fernando Mota, Juan J. Novoa, Matteo Farnesi Camellone, Stefano Fabris, Remco W. A. Havenith, Ria Broer, Jordi Ribas-Arino*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

1 Citation (Scopus)

Abstract

Materials based on regular π-stacks of planar organic radicals are intensively pursued by virtue of their technologically relevant properties. Yet, these π-stacks are commonly unstable against π-dimerization. In this computational study, we reveal that regular π-stacks of planar dithiazolyl radicals can be rendered stable, in some range of temperatures,viatwo different mechanisms. When the radicals of a π-stack are both longitudinally and latitudinally slipped with respect to each other, the corresponding regular π-stacked configuration is associated with a locally stable minimum in the potential energy surface of the system. Conversely, those regular π-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 π-dimers, translates into two different ways of exploiting spin-Peierls-like transitions in switchable dithiazolyl-based materials.

Original languageEnglish
Pages (from-to)5437-5448
Number of pages12
JournalJournal of Materials Chemistry C
Volume8
Issue number16
DOIs
Publication statusPublished - 28-Apr-2020

Keywords

  • MAGNETIC-PROPERTIES
  • BISDITHIAZOLYL RADICALS
  • MOLECULAR MATERIALS
  • SPIN TRANSITIONS
  • BASIS-SETS
  • BISTABILITY
  • PSEUDOPOTENTIALS
  • EXCHANGE
  • VALENCE
  • LONG

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