Metal-free atom transfer radical polymerization with ppm catalyst loading under sunlight

Qiang Ma; Jinshuai Song; Xun Zhang; Yu Jiang; Li Ji; Saihu Liao

doi:10.1038/s41467-020-20645-8

Metal-free atom transfer radical polymerization with ppm catalyst loading under sunlight

Nat Commun. 2021 Jan 18;12(1):429. doi: 10.1038/s41467-020-20645-8.

Authors

Qiang Ma¹, Jinshuai Song², Xun Zhang¹, Yu Jiang¹, Li Ji³, Saihu Liao^{4

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Affiliations

¹ Key Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou, 350108, China.
² College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, 450001, China.
³ Grubbs Institute, Southern University of Science and Technology, Shenzhen, 518055, China.
⁴ Key Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou, 350108, China. shliao@fzu.edu.cn.
⁵ State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, 350108, China. shliao@fzu.edu.cn.
⁶ Beijing National Laboratory of Molecular Science (BNLMS), Beijing, 100190, China. shliao@fzu.edu.cn.

Abstract

Organocatalytic atom transfer radical polymerization (O-ATRP) is recently emerging as an appealing method for the synthesis of metal-free polymer materials with well-defined microstructures and architectures. However, the development of highly effective catalysts that can be employed at a practical low loading are still a challenging task. Herein, we introduce a catalyst design logic based on heteroatom-doping of polycyclic arenes, which leads to the discovery of oxygen-doped anthanthrene (ODA) as highly effective organic photoredox catalysts for O-ATRP. In comparison with known organocatalysts, ODAs feature strong visible-light absorption together with high molar extinction coefficient (ε_455nm up to 23,950 M^-1 cm^-1), which allow for the establishment of a controlled polymerization under sunlight at low ppm levels of catalyst loading.