Search for: All records

Naphthopyran molecular switches undergo a ring-opening reaction upon external stimulation to generate intensely colored merocyanine dyes. Their unique modularity and synthetic accessibility afford exceptional control over their properties and stimuli-responsive behavior. Commercial applications of naphthopyrans as photoswitches in photochromic ophthalmic lenses have spurred an extensive body of work exploring naphthopyran–merocyanine structure–property relationships. The recently discovered mechanochromic behavior of naphthopyrans has led to their emergent application in the field of polymer mechanochemistry, enabling advances in the design of force-responsive materials as well as fundamental insights into mechanochemical reactivity. The structure–property relationships established in the photochemical literature serve as a convenient blueprint for the design of naphthopyran molecular force probes with precisely tuned properties. On the other hand, the mechanochemical reactivity of naphthopyran diverges in many cases from the conventional photochemical pathways, resulting in unexpected properties and opportunities for deeper understanding and innovation in polymer mechanochemistry. Here, we highlight the features of the naphthopyran scaffold that render it a powerful platform for the design of mechanochromic materials and review recent advances in naphthopyran mechanochemistry. 

In contrast to common angular naphthopyrans that exhibit strong photochromic and mechanochromic behavior, constitutionally isomeric linear naphthopyrans are typically not photochromic, due to the putative instability of the completely dearomatized merocyanine product. The photochemistry of linear naphthopyrans is thus relatively understudied compared to angular naphthopyrans, while the mechanochromism of linear naphthopyrans remains completely unexplored. Here we demonstrate that the incorporation of a polarizing dialkylamine substituent enables photochromic and mechanochromic behavior from polymers containing a novel linear naphthopyran motif. In solution phase experiments, a Lewis acid trap was necessary to observe accumulation of the merocyanine product upon photochemical and ultrasound-induced mechanochemical activation. However, the same linear naphthopyran molecule incorporated as a crosslinker in polydimethylsiloxane elastomers renders the materials photochromic and mechanochromic without the addition of any trapping agent. This study provides insights into the photochromic and mechanochromic reactivity of linear naphthopyrans that have conventionally been considered functionally inert, adding a new class of naphthopyran molecular switches to the repertoire of stimuli-responsive polymers. 

Multimodal mechanophores that react under mechanical force to produce discrete product states with uniquely coupled absorption properties are interesting targets for the design of force-sensing polymers. Herein, we investigate the reactivity of a 2H-bis-naphthopyran mechanophore that generates thermally persistent mono-merocyanine and bis-merocyanine products upon mechanical activation in solution using ultrasonication, distinct from the thermally reversible products generated photochemically. We demonstrate that a force-mediated ester C(O)–O bond scission reaction following ring opening establishes an intramolecular hydrogen bond, locking one merocyanine subunit in the open form. Model compound studies suggest that this locked subunit confers remarkable thermal stability to bis-merocyanine isomers possessing a trans exocyclic alkene on the other subunit, implicating the formation of an unusual trans merocyanine isomer as the product of mechanochemical activation. Density functional theory calculations unexpectedly predict a thermally reversible retro-cyclization reaction of the bis-merocyanine species that could explain the mechanochemical generation of the unusual trans merocyanine isomer. 

Understanding structure–mechanochemical reactivity relationships is important for informing the rational design of new stimuli-responsive polymers. To this end, establishing accurate reaction kinetics for mechanophore activation is a key objective. Here, we validate an initial rates method that enables the accurate and rapid determination of rate constants for ultrasound-induced mechanochemical transformations. Experimental reaction profiles are well-aligned with theoretical models, which support that the initial rates method effectively deconvolutes the kinetics of specific mechanophore activation from the competitive process of nonspecific chain scission.