Side‐Chain Control of Topochemical Polymer Single Crystals with Tunable Elastic Modulus

Topochemical polymerizations hold the promise of producing high molecular weight and stereoregular single crystalline polymers by first aligning monomers before polymerization. However, monomer modifications often alter the crystal packing and result in non-reactive polymorphs. Here, we report a systematic study on the side chain functionalization of the bis(indandione) derivative system that can be polymerized under visible light. Precisely engineered side chains help organize the monomer crystals in a one-dimensional fashion to maintain the topochemical reactivity. By optimizing the side chain length and end group of monomers, the elastic modulus of the resulting polymer single crystals can also be greatly enhanced. Lastly, using ultrasonication, insoluble polymer single crystals can be processed into free-standing and robust polymer thin films. This work provides new insights on the molecular design of topochemical reactions and paves the way for future applications of this fascinating family of materials.