Cold photo-carving of halogen-bonded co-crystals of a dye and a volatile co-former using visible light

The formation of co-crystals by the assembly of molecules with complementary molecular recognition functionalities is a popular strategy to design or improve a range of solid-state properties, including those relevant for pharmaceuticals, photo- or thermoresponsive materials and organic electronics. Here, we report halogen-bonded co-crystals of a fluorinated azobenzene derivative with a volatile component-either dioxane or pyrazine-that can be cut, carved or engraved with low-power visible light. This cold photo-carving process is enabled by the co-crystallization of a light-absorbing azo dye with a volatile component, which gives rise to materials that can be selectively disassembled with micrometre precision using low-power, non-burning laser irradiation or a commercial confocal microscope. The ability to shape co-crystals in three dimensions using laser powers of 0.5-20 mW-substantially lower than those used for metals, ceramics or polymers-is rationalized by photo-carving that targets the disruption of weak supramolecular interactions, rather than the covalent bonds or ionic structures targeted by conventional laser beam or focused ion beam machining processes.

Automated summary

Cold photo-carving using low-power visible light enabled by halogen-bonded co-crystals allows for selective disassembly of materials, leading to three-dimensional shaping.