The marriage of dual-acceptor strategy and C-H activation polymerization:naphthalene diimide-based n-type polymers with adjustable molar mass and decent performance  

作　　者：Ying-Han Zhao Wenhao Li Tao Shen Yan Zhao Yunqi Liu Yang Wang 

机构地区：[1]Laboratory of Molecular Materials and Devices,Department of Materials Science,Fudan University,Shanghai,200438,China [2]Beijing National Laboratory for Molecular Sciences,Key Laboratory of Organic Solids,Institute of Chemistry,Chinese Academy of Sciences,Beijing,100190,China

出　　处：《Science China Chemistry》2023年第2期548-561,共14页中国科学（化学英文版）

基　　金：supported by the National Key R&D Program of China(2018YFA0703200);the National Natural Science Foundation of China(61890940,51903051);the support by the Natural Science Foundation of Shanghai(21ZR1406900);the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning(SSH2021010)。

摘　　要：The development of readily accessible high-mobility n-type semiconducting polymers is in great demand for realizing highperformance p-n junction-based organic electronics.In this study,we demonstrate that with the combination of dual-acceptor strategy and C-H direct arylation polymerization(DAr P),unipolar n-type semiconducting polymers can be conveniently synthesized.By tuning the monomer concentration,three dual-acceptor polymers,namely,poly(naphthalene diimide-alt-dithiophenyl pyrrolopyrrole-dione)(PNDI-DPP),poly(naphthalene diimide-alt-dithiophenyl isoindigo)(PNDI-IID),and poly(naphthalene diimide-alt-dithiophenyl bezothiadiazole)(PNDI-BT)can be obtained via C-H activation with decent number average molecular weight of~10 to 30 kg mol^(-1)and relatively narrow polydispersity index of~2.In addition,these polymers are defect-free in nature as evidenced by the nuclear magnetic resonance.Moreover,we attribute the different molar masses of the three copolymers under the same DAr P condition to the differentα-C-H acidity,which may stem from different electronwithdrawing capability of the hydrogenated acceptor units.Furthermore,the influence of the hydrogenated acceptor monomers on the optical,electrochemical and charge transporting properties is comprehensively studied.Among the three dual-acceptor polymers,PNDI-BT demonstrates the highest electron mobilities of up to 0.6 cm^(2)V^(-1)s^(-1)in unipolar n-type organic transistors because of its relatively planar backbone,larger overlaps of the lowest unoccupied molecular orbital and strong H-aggregation.Note that the transistor performance of PNDI-BT synthesized via C-H activation in this study is at least comparable to the one made by conventional C(sp^(2))-C(sp^(2))Stille or Suzuki cross-coupling polymerization.This study demonstrates the presented protocol can be a useful platform for sustainable and convenient synthesis of high-performance n-type semiconducting polymers.

关 键 词：n-type polymers C-H activation dual-acceptor strategy naphthalene diimide organic thin-film transistors 

分 类 号：O621.251[理学—有机化学]