Modulating Polymer Dispersity with Light: Cationic Polymerization of Vinyl Ethers Using Photochromic Initiators

Deterministic methods for tuning polymer dispersity are rare, especially for nonradical polymerizations. Reported here is the first example of photomodulating dispersity in controlled cationic polymerizations of vinyl ethers using carboxy‐functionalized dithienylethene initiators. Reversible photoisomerization of these initiators induces changes in their acidities by up to an order of magnitude. Using the more acidic, ring‐closed isomers as initiators results in polymers with lower dispersities. The degree of light‐induced pK_a change in the initiators correlates with the degree of dispersity change in polymers derived from the isomeric initiators. The polymerizations are controlled, and dynamic photoswitching of dispersity during the polymerization reaction was demonstrated. This work provides a framework for photomodulating dispersity in other controlled polymerizations and developing one‐pot block copolymerization reactions in which the dispersities of component blocks can be controlled using light.