Mechanical Actuation and Patterning of Rewritable Crystalline Monomer−Polymer Heterostructures via Topochemical Polymerization in a Dual-Responsive Photochromic Organic Material

The dark-orange monomer single crystals of 1,1′-dioxo-1H-2,2′-biindene-3,3′-diyldidodecanoate (BIT-dodeca2) convert to a transparent single-crystalline polymer (PBIT-dodeca2) material via a single-crystal-to-single-crystal (SCSC) polymerization reaction under sunlight, which then undergoes reverse thermal transformation into BIT-dodeca2 single crystals, leading to reversible photo-/thermochromism, coupled with mechanical actuation. We exploit the properties of this unique material to demonstrate the formation of monomer–polymer heterostructures in selected regions of single crystals with micrometer-scale precision using a laser. This is the first example of heterostructure patterning involving monomer–polymer domains in single crystals. We reveal that the speed of photomechanical bending induced by the polymerization reaction in this example is comparable to those of the well-known diarylethene derivatives, in which electrocyclic ring-closing–ring-opening reactions operate. Furthermore, we characterize the distinct mechanical properties of the monomer and polymer using a quantitative nanoindentation technique as well as demonstrate photopatterning on a monomer-coated paper for potential use in security devices. These crystals with several advantages, such as photomechanical bending (weight lifting) even when the crystal size is large, responsiveness to both UV and visible light, distinct solubilities (the polymer is insoluble, whereas the monomer is soluble in most organic solvents) and colors, provide unique opportunities for their use at different length scales of the sample (μm to mm) for various purposes.