A Tricyclic Framework with Integrated B←N and Cyano Dual Functionalization for Superior n-Type Organic Electronics.

Angew Chem Int Ed Engl

Department of Materials Science, State Key Laboratory of Molecular Engineering of Polymers, Fudan University, 2005, Songhu Road, Shanghai, 200438, China.

Published: October 2024

AI Article Synopsis

  • n-Type conjugated polymers with low-lying LUMO energy levels are crucial for the development of high-performance organic thin-film transistors (OTFTs) and thermoelectrics (OTEs).
  • Researchers used a strategy of peripheral functionalization on anthracene, introducing dual BF2/B(CN)2 groups to enhance electron-withdrawing capabilities, resulting in two new acceptor building blocks: DBNF and DBNCN.
  • The copolymers PDBNF and PDBNCN display improved electron mobility and conductivity, with PDBNF achieving a LUMO of around -4.0 eV and PDBNCN exhibiting exceptional conductivity and power factor, making them highly effective for n-doping

Article Abstract

n-Type conjugated polymers featuring low-lying lowest unoccupied molecular orbital (LUMO) energy levels are essential for achieving high-performance n-type organic thin-film transistors (OTFTs) and organic thermoelectrics (OTEs). However, the synthesis of acceptors with strong electron-withdrawing characteristics presents a significant challenge. Herein, a peripheral functionalization strategy is employed on the tricyclic framework anthracene by introducing dual N,O-bidentate BF/B(CN) groups to enhance its electron-withdrawing capability. This approach successfully navigates synthetic challenges, leading to the development of two novel acceptor building blocks: DBNF and DBNCN. Compared to the counterparts with a single N,O-bidentate BF/B(CN) moiety, DBNF and DBNCN exhibit an extended π-backbone, enhanced molecular packing, and improved electron-withdrawing properties. Utilizing these innovative acceptor monomers, copolymers, PDBNF and PDBNCN, are synthesized, which exhibit considerably suppressed LUMO ≈-4.0 eV. The deep LUMO of PDBNF together with its favourable bimodal packing orientation leads to remarkable electron mobility of 3.04 cm V s with improved stability in OTFTs. Importantly, efficient n-doping in OTEs is achieved with PDBNCN, exhibiting exceptional conductivity of 95.5 S cm and a maximum power factor of 147.8 μW m K-among the highest reported for solution-processed n-type polymers. This work underscores the effectiveness of introducing dual B←N and cyano functionalities in attaining high-performance n-type plastic electronics.

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http://dx.doi.org/10.1002/anie.202416669DOI Listing

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