Abstract
To improve the control and precision in polymer synthesis, the development of polymerization with logical control by multiple stimuli has attracted considerable attention in recent years. Herein, we describe the introduction of a dual regulation by light and pH to organocatalytic atom transfer radical polymerization (O-ATRP), which features mild pH conditions, visible light irradiation, transition metal-free products, and excellent on/off control by both pH and light. 1,1-Binaphthol (BINOL) was successfully identified as a class of pH-responsive photoredox catalysts for O-ATRP, and show readily tunable photophysical properties and highly reversible chromic shift of maximum absorption (up to 60 nm) by very mild pH-mediation (pH 5/7). Moreover, the unique pH-responsive feature of BINOL also inspires the discovery of simple phenols like naphthol and pyrenol that could also drive the radical polymerization under light and afford higher catalytic efficiency and better control upon basic mediation. Given the widespread presence of phenols in natural compounds, we anticipate this work could also draw greater attention to their potential pH-responsive photophysical properties or other roles in catalysis or life systems.
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Acknowledgements
We gratefully acknowledge the financial support from the National Natural Science Foundation of China (22371240, 22361132535 & 22173083), Arawana Charity Foundation, Xiamen University, the Recruitment Program of Global Experts and Fuzhou University. Special thanks to the members of the Analysis and Testing Center of the College of Chemistry and Chemical Engineering for their excellent service. We thank Mr. Xipao Chen (Ningbo Institute of Materials Technology & Engineering, CAS) and Mr. Jianbin Chen (Key Laboratory of Spectrochemical Analysis & Instrumentation, College of Chemistry and Chemical Engineering, Xiamen University) for their help in the photoluminescence-related testing and discussions.
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Jiang, Y., Ma, Q., Chen, J. et al. Organocatalytic atom transfer radical polymerization with light and pH dual-gated regulation. Nat Commun (2026). https://doi.org/10.1038/s41467-026-72610-6
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DOI: https://doi.org/10.1038/s41467-026-72610-6
