Cyano-Functionalized Pyrazine: A Structurally Simple and Easily Accessible Electron-Deficient Building Block for n-Type Organic Thermoelectric Polymers

초록

Developing low-cost and high-performance n-type polymer semiconductors is essential to accelerate the application of organic thermoelectrics (OTEs). To achieve this objective, it is critical to design strong electron-deficient building blocks with simple structure and easy synthesis, which are essential for the development of n-type polymer semiconductors. Herein, we synthesized two cyano-functionalized highly electron-deficient building blocks, namely 3,6-dibromopyrazine-2-carbonitrile (CNPz) and 3,6-Dibromopyrazine-2,5-dicarbonitrile (DCNPz), which feature simple structures and facile synthesis. CNPz and DCNPz can be obtained via only one-step reaction and three-step reactions from cheap raw materials, respectively. Based on CNPz and DCNPz, two acceptor-acceptor (A-A) polymers, P(DPP-CNPz) and P(DPP-DCNPz) are successfully developed, featuring deep-positioned lowest unoccupied molecular orbital (LUMO) energy levels, which are beneficial to n-type organic thin-film transistors (OTFTs) and OTEs performance. An optimal unipolar electron mobility of 0.85 and 1.85 cm2 V-1 s-1 is obtained for P(DPP-CNPz) and P(DPP-DCNPz), respectively. When doped with N-DMBI, P(DPP-CNPz) and P(DPP-DCNPz) show high n-type electrical conductivities/power factors of 25.3 S cm-1/41.4 mu W m-1 K-2, and 33.9 S cm-1/30.4 mu W m-1 K-2, respectively. Hence, the cyano-functionalized pyrazine CNPz and DCNPz represent a new class of structurally simple, low-cost and readily accessible electron-deficient building block for constructing n-type polymer semiconductors. Two simple structure and highly electron-deficient building blocks (CNPz and DCNPz) were synthesized and incorporated into polymer backbone. P(DPP-CNPz) and P(DPP-DCNPz) show unipolar electron mobilities of 0.85 and 1.85 cm2 V-1 s-1 in OTFTs, respectively. When doped with N-DMBI, these two polymers exhibit electrical conductivities and power factors of 25.3 S cm-1/41.4 mu W m-1 K-2, and 33.9 S cm-1/30.4 mu W m-1 K-2.+ image

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