Naphthopyran molecular switches and their emergent mechanochemical reactivity.

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.

Competitive Activation Experiments Reveal Significantly Different Mechanochemical Reactivity of Furan-Maleimide and Anthracene-Maleimide Mechanophores.

During the past two decades, our understanding of mechanochemical reactivity has advanced considerably. Nevertheless, an incomplete knowledge of structure-activity relationships and the principles that govern mechanochemical transformations limits molecular design. The experimental development of mechanophores has thus benefited from simple computational tools like CoGEF, from which quantitative metrics like rupture force can be extracted to estimate reactivity.

Validation of an Accurate and Expedient Initial Rates Method for Characterizing Mechanophore Reactivity.

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.

Mechanically gated formation of donor-acceptor Stenhouse adducts enabling mechanochemical multicolour soft lithography.

Stress-sensitive molecules called mechanophores undergo productive chemical transformations in response to mechanical force. A variety of mechanochromic mechanophores, which change colour in response to stress, have been developed, but modulating the properties of the dyes generally requires the independent preparation of discrete derivatives. Here we introduce a mechanophore platform enabling mechanically gated multicolour chromogenic reactivity.

Examining the Impact of Relative Mechanophore Activity on the Selectivity of Ultrasound-Induced Mechanochemical Chain Scission.

Despite recent advances in polymer mechanochemistry, a more complete understanding of the factors that dictate the ultrasound-induced mechanochemical activation efficiency of mechanophores is necessary. Here, we examine how the identity of a mechanophore, and hence its unique force-coupled reactivity, affects the competition between mechanophore activation and nonspecific polymer backbone scission. Polymers incorporating distinct mechanophores but with putatively similar "chain-centeredness" exhibit widely different mechanochemical activation efficiencies.

Colloidal Covalent Organic Frameworks.

Covalent organic frameworks (COFs) are two- or three-dimensional (2D or 3D) polymer networks with designed topology and chemical functionality, permanent porosity, and high surface areas. These features are potentially useful for a broad range of applications, including catalysis, optoelectronics, and energy storage devices. But current COF syntheses offer poor control over the material's morphology and final form, generally providing insoluble and unprocessable microcrystalline powder aggregates.

Insight into the crystallization of amorphous imine-linked polymer networks to 2D covalent organic frameworks.

We explore the crystallization of a high surface area imine-linked two-dimensional covalent organic framework (2D COF). The growth process reveals rapid initial formation of an amorphous network that subsequently crystallizes into the layered 2D network. The metastable amorphous polymer may be isolated and resubjected to growth conditions to form the COF.