Photoinduced Clusteroluminescence Redshift of Poly(methyl acrylate) via Radicals

One-step photopolymerization and photochromism of clusteroluminescence (CL) polymers mean that the polymer materials can be prepared on a large scale and applied widely. Herein, we reported unique photochromic CL polymers prepared by one-step radical photopolymerization. Seven copolymerized films (PMABA) with methyl acrylate and butyl acrylate as monomers, a cross-linked PMA (PMA-CL) film, a double-network PMAPBA film based on the first network PMA-CL, and four PMA films with increasing content of photoinitiator ethoxy benzoin (BEE) were prepared to study CL formation and transition. Experimental results prove that increasing the ratio of the PMA chains in PMABA enhances the photochromic effect, which verifies the main role of PMA chains with the shorter branched alkanes. Surprisingly, cross-linking in PMA-CL strengthens interchain packing and interchain through-space interactions (TSIs), leading to the formation of larger clusters and further CL redshift from 410 to 491 nm, whereas the PBA chains filled in the cross-linked network weakens interchain TSIs among PMA chains and makes CL red shift from 410 to 472 nm. In addition, as the BEE content increases in the PMA films, a higher radical concentration also promotes the formation of TSIs and clusters, which benefits the photochromism. For applications, colorless, dissolvable, and thermoplastic PMA featuring photochromism in this case can be widely used in information loading, rewriting, and multifunctional coating. This work provides a new strategy to enrich the properties of CL polymers toward diverse applications.