Single-Crystal Linear Polymers Through Visible Light–Triggered Topochemical Quantitative Polymerization

One of the challenges in polymer science has been to prepare large-polymer single crystals. We demonstrate a visible light-triggered quantitative topochemical polymerization reaction based on a conjugated dye molecule. Macroscopic-size, high-quality polymer single crystals are obtained. Polymerization is not limited to single crystals, but can also be achieved in highly concentrated solution or semicrystalline thin films. In addition, we show that the polymer decomposes to monomer upon thermolysis, which indicates that the polymerization-depolymerization process is reversible. The physical properties of the polymer crystals enable us to isolate single-polymer strands via mechanical exfoliation, which makes it possible to study individual, long polymer chains.