A Fully Coplanar Donor–Acceptor Polymeric Semiconductor with Promoted Charge Separation Kinetics for Photochemistry

Charge generation and separation are regarded as the major constraints limiting the photocatalytic activity of polymeric photocatalysts. Herein, two new linear polyarylether‐based polymers (PAE–CPs) with distinct linking patterns between their donor and acceptor motifs were tailor‐made to investigat...

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Published in:Angewandte Chemie International Edition 2021-07, Vol.60 (30), p.16355-16359
Main Authors: Lan, Zhi‐An, Wu, Meng, Fang, Zhongpu, Chi, Xu, Chen, Xiong, Zhang, Yongfan, Wang, Xinchen
Format: Article
Language:English
Subjects:
Catalytic activity
Design modifications
Electromagnetic absorption
Electronics industry
hydrogen evolution
hydrogen peroxide evolution
linking pattern
Organic semiconductors
Photocatalysis
Photochemistry
polyarylether
Polymers
Separation
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Summary:Charge generation and separation are regarded as the major constraints limiting the photocatalytic activity of polymeric photocatalysts. Herein, two new linear polyarylether‐based polymers (PAE–CPs) with distinct linking patterns between their donor and acceptor motifs were tailor‐made to investigate the influence of different linking patterns on the charge generation and separation process. Theoretical and experimental results revealed that compared to the traditional single‐stranded linker, the double‐stranded linking pattern strengthens donor–acceptor interactions in PAE–CPs and generates a coplanar structure, facilitating charge generation and separation, and enabling red‐shifted light absorption. With these prominent advantages, the PAE–CP interlinked with a double‐stranded linker exhibits markedly enhanced photocatalytic activity compared to that of its single‐strand‐linked analogue. Such findings can facilitate the rational design and modification of organic semiconductors for charge‐induced reactions. Two polyarylether‐based polymers with single/double linking patterns were investigated to establish the effect of the linking patterns on the charge generation and separation process in D–A conjugated polymer photocatalysts, thus achieving remarkable photocatalytic HER and HPER performances.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202103992