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

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...

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Published inJournal of materials chemistry. C, Materials for optical and electronic devices Vol. 8; no. 16; pp. 5437 - 5448
Main 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
Format Journal Article
LanguageEnglish
Published Cambridge Royal Society of Chemistry 30.04.2020
Subjects
Computer simulation
Configurations
Dimerization
Dimers
Ellipsoids
Potential energy
Radicals
Stabilization
Stacks
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Summary: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. Regular π-stacks of dithiazolyl radicals can be rendered stable via two different mechanisms depending on the relative disposition of neighboring radicals.
Bibliography:10.1039/d0tc00634c
3.2 Å (Fig. S10 and S11). Minimum energy paths connecting configurations A and C through configuration B for PDTA and TDPDTA (Fig. S12). Energy decomposition analysis of the interaction energy between TDPDTA and PDTA radicals (Tables S2 and S3). See DOI
Electronic supplementary information (ESI) available. The ESI includes: views of crystal packing of LT and HT polymorphs of PDTA and TDPDTA (Fig. S1 and S2). Supercells used in optimizations and dynamics of LT and HT polymorphs of PDTA and TDTDTA (Fig. S3 and S4). Comparison between experimental and optimized LT polymorph of PDTA and TDPDTA (Fig. S5 and S6). Comparison between experimental and calculated thermal ellipsoids of PDTA and TDPDTA (Table S1 and Fig. S7 and S8). AIMD simulations of the LT polymorphs of PDTA and TDPDTA (Fig. S9). 2D-PES of isolated π-dimer of TDPDTA radicals at
d
3.2 and 3.1 Å and PDTA at
IP
ISSN:2050-7526
2050-7534
DOI:10.1039/d0tc00634c