Diselenide Bonds as an Alternative to Outperform the Efficiency of Disulfides in Self-Healing Materials

Self-healing materials are a very promising kind of materials due to their capacity to repair themselves. Among others, dichalcogenide-based materials are widely studied due to their dynamic covalent bond nature. Recently, the reaction mechanism occurring in these materials was characterized both theoretically and experimentally. In this vein, a theoretical protocol was established in order to predict further improvements. Among these improvements, the use of diselenides instead of disulfides appears to be one of the paths to enhance these properties. Nevertheless, the physicochemical aspects of these improvements are not completely clear. In this work, the self-healing properties of several disulfides, diselenides, and mixed S–Se materials have been considered by means of computational simulations. Among all the tested species, diphenyl diselenide based materials appear to be the most promising ones due to the decrease on the reaction barriers, instead of weaker diselenide bonds, as thought up to now. Moreover, the radical formation needed in this process would also be enhanced by the fact that these species are able to absorb visible light. In this manner, at room conditions, selenyl radicals would be formed by both thermal dissociation and photodissociation. This fact, together with the lower energetic barriers needed for the diselenide exchange, makes diphenyl diselenides ideal for self-healing materials.