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Fluorescent polymers are key components of advanced optoelectronics; however, strong donor–acceptor (D–A) charge transfer often leads to intense visible-light absorption, limiting their use in transparent optical devices. Herein, we report the synthesis of triarylamine (TAA)-based polyesters via ring-opening alternating copolymerization (ROAC) of TAA-based anhydrides with epoxides of various rigidities. ROAC converts anhydride fluorophores into diester linkages, weakens the D–A charge-transfer interactions, and shifts absorption into the ultraviolet region, affording colorless transparent films. In solution, the photoluminescence quantum yield (PLQY) is strongly influenced by polymer backbone rigidity. In the solid state, side-chain engineering enables precise tuning of emission color. Notably, ether-containing side chains induce bathochromic shifts of 14–21 nm via inter- and intrachain aromatic C–H···O interactions without compromising intrinsic PLQY. We show that polyesters prepared via ROAC exhibit perfectly alternating monomer sequences and provide a versatile platform for the fabrication of colorless films with tunable solid-state emission.
Shao et al. (Thu,) studied this question.