Hydrated Hydroxide Complex Dominates the AIE Properties of Nonconjugated Polymeric Luminophores

Nontraditional intrinsic luminescence (NTIL) which always accompanied with aggregation-induced emission (AIE) features has received considerable attention due to their importance in the understanding of basic luminescence principle and potential practical applications. However, the rational modulation of the NTIL of nonconventional luminophores remains difficult, on account of the limited understanding of emission mechanisms. Herein, the emission color of nonconjugated poly(methyl vinyl ether-alt-maleic anhydride) (PMVEMA) can be readily regulated from blue to red by controlling the alkalinity during the hydrolysis process. The nontraditional photoluminescence with AIE property is from the new formed p-band state, resulting from the strong overlapping of p orbitals of the clustered O atoms through space interactions. Hydrated hydroxide complexes embedded in the entangled polymer chain make big difference on the clustering of O atoms which dominates the AIE property of nonconjugated PMVEMA. These new insights into the photoluminescence mechanism of NTIL should stimulate additional experimental and theoretical studies and can benefit the molecular-level design of nontraditional chromophores for optoelectronics and other applications.

Automated summary

Nontraditional intrinsic luminescence (NTIL) with aggregation-induced emission (AIE) features has attracted attention due to their importance in understanding basic luminescence principles and potential applications. However, the modulation of nonconventional luminophores remains difficult due to limited understanding of their emission mechanisms. In this study, the emission color of nonconjugated poly(methyl vinyl ether-alt-maleic anhydride) (PMVEMA) could be easily controlled from blue to red by adjusting the alkalinity during the hydrolysis process. The nontraditional photoluminescence with AIE property is attributed to the new formed p-band state resulting from strong overlapping of clustered O atoms through space interactions. The O atom clustering, dominated by hydrated hydroxide complexes in the entangled polymer chain, plays a crucial role in the AIE property of nonconjugated PMVEMA. These findings contribute to further experimental and theoretical studies and can aid in the molecular-level design of nontraditional chromophores for optoelectronics and other applications.