Heteroatom-facilitated blue to near-infrared emission of nonconjugated polyesters

Making nonconjugated polymers to emit visible light remains a formidable challenge, let alone near-infrared (NIR) light, although NIR luminophores have many advanced applications. Herein, we propose an electron-bridging strategy of using heteroatoms (O, N, and S) to achieve tunable emission from blue to NIR regions (440-800 nm) in nonconjugated polyesters. Especially, sulfur-containing polyester P4 exhibits NIR clusteroluminescence (CL) on changing either the concentration or excitation wavelength. Experimental characterization and theoretical calculation demonstrate that the introduction of heteroatoms significantly enhances the through-space interactions (TSIs) <i>via</i> the electron-bridging effect between heteroatoms and carbonyls. The strength of the electron-bridging effect follows the order of S > N > O, based on two synergistic effects: electronic structure and van der Waals radius of heteroatoms. This work provides a low-cost, scalable platform to produce new-generation nonconjugated luminophores with deeper insight into the photophysical mechanism.