Citation: Yan-hou Geng, Ying Sui. Direct Arylation Polycondensation Synthesis of High Mobility Conjugated Polymers[J]. Acta Polymerica Sinica, ;2019, 50(2): 109-117. doi: 10.11777/j.issn1000-3304.2018.18231 shu

Direct Arylation Polycondensation Synthesis of High Mobility Conjugated Polymers

Yan-hou Geng ^, ,
Ying Sui

School of Materials Science and Engineering, Tianjin University, Tianjin 300072

Corresponding author: Yan-hou Geng, yanhou.geng@tju.edu.cn
Received Date: 3 November 2018
Revised Date: 28 November 2018
Available Online: 18 December 2018

A new protocol for conjugated polymer synthesis, direct arylation polycondensation (DArP) bears the merits of more straightforwardness (fewer steps), better atom economy, and greater environmental benignity, but still faces remaining challenges in reactivity and selectivity. Given that high mobility conjugated polymers are receiving added attention these days due to their extensive use in organic thin-film transistors (OTFTs), this feature article briefly introduces the underlying mechanism of direct arylation reaction and systematically summarizes the application of DArP in synthesizing polythiophenes and donor-acceptor (D-A) conjugated polymers from naphthalene diimide (NDI), diketopyrrolopyrrole (DPP), and isoindigo (IID) derivatives. The α C―H direct arylation of thiophene rings can give rise to conjugated polymers based on NDI and DPP derivatives, which exhibit negligible defects and reasonably high molecular weights through careful optimization of the catalyst (including ligands), solvent, additives, monomer concentration, and polymerization temperature. To deal with side reactions during DArP, primarily the C―H/C―H and C―Br/C―Br homo-couplings and the β C―H direct arylation (causing branching or cross-linking), multi-fluorinated thiophene moieties such as 3,3',4,4'-tetrafluoro-2,2'-bithiophene (4F2T) and (E)-1,2-bis(3,4-difluorothien-2-yl)ethene (4FTVT) have been designed for a higher reactivity toward DArP. Moreover, selectivity issues can be well sidestepped by introducing F-atoms onto the β-positions of thiophene unit, which in the meantime significantly lowers the frontier molecular orbital energy levels of polymers obtained. In consequence, ambipolar or unipolar n-type D-A conjugated polymers based on DPP and IID derivatives can be harvested at high molecular weight, which enables further fabrication of ambipolar OTFTs with hole and electron mobilities individually up to 2.63 and 8.11 cm² V⁻¹ s⁻¹ or unipolar n-type OTFTs with electron mobility over 4 cm² V⁻¹ s⁻¹. Progress above indicates that DArP can afford high mobility and defect-free conjugated polymers through elaborate monomer design and the optimal polymerization conditions. Hence, DArP can serve as a reliable method for the mass production of high performance conjugated polymers.
- Direct arylation polycondensation,
- Conjugated polymers,
- Semiconducting materials,
- Organic thin-film transistors,
- Charge carrier mobility
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沈阳化工大学材料科学与工程学院沈阳 110142

Direct Arylation Polycondensation Synthesis of High Mobility Conjugated Polymers

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

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通讯作者: 陈斌, bchen63@163.com