Two different mechanisms of stabilization of regular π-stacks of radicals in switchable dithiazolyl-based materials. Issue 16 (30th March 2020)

• Record Type: Journal Article
• Authors: Francese, Tommaso; Vela, Sergi; Deumal, Mercè; Mota, Fernando; Novoa, Juan J.; Camellone, Matteo Farnesi; Fabris, Stefano; Havenith, Remco W. A.; Broer, Ria; Ribas-Arino, Jordi
• Is Part Of: Journal of materials chemistry. Volume 8:Issue 16(2020)
• Page Start: 5437
• Page End: 5448
• Publication Date: 2020-03-30
• Subjects: Materials -- Periodicals; Chemistry, Analytic -- Periodicals; Optical materials -- Research -- Periodicals; Electronics -- Materials -- Research -- Periodicals; 543.0284
• DOI: 10.1039/d0tc00634c
• Languages: English
• ISSNs: 2050-7526

Abstract

Abstract : Regular π-stacks of dithiazolyl radicals can be rendered stable via two different mechanisms depending on the relative disposition of neighboring radicals. 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, via two 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.