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Synthesis of Vinylene-Linked Two-Dimensional Conjugated Polymers via the Horner-Wadsworth-Emmons Reaction.
Angewandte Chemie International Edition ( IF 16.6 ) Pub Date : 2020-09-22 , DOI: 10.1002/anie.202010398
Dominik L Pastoetter 1 , Shunqi Xu 1 , Mino Borrelli 1 , Matthew Addicoat 2 , Bishnu P Biswal 3 , Silvia Paasch 4 , Arezoo Dianat 5 , Heidi Thomas 6 , Reinhard Berger 1 , Sebastian Reineke 6 , Eike Brunner 4 , Gianaurelio Cuniberti 5 , Marcus Richter 1 , Xinliang Feng 1
Affiliation  

In this work, we demonstrate the first synthesis of vinylene‐linked 2D CPs, namely, 2D poly(phenylenequinoxalinevinylene)s 2D‐PPQV1 and 2D‐PPQV2, via the Horner–Wadsworth–Emmons (HWE) reaction of C2‐symmetric 1,4‐bis(diethylphosphonomethyl)benzene or 4,4′‐bis(diethylphosphonomethyl)biphenyl with C3‐symmetric 2,3,8,9,14,15‐hexa(4‐formylphenyl)diquinoxalino[2,3‐a:2′,3′‐c]phenazine as monomers. Density functional theory (DFT) simulations unveil the crucial role of the initial reversible C−C single bond formation for the synthesis of crystalline 2D CPs. Powder X‐ray diffraction (PXRD) studies and nitrogen adsorption‐desorption measurements demonstrate the formation of proclaimed crystalline, dual‐pore structures with surface areas of up to 440 m2 g−1. More importantly, the optoelectronic properties of the obtained 2D‐PPQV1 (Eg=2.2 eV) and 2D‐PPQV2 (Eg=2.2 eV) are compared with those of cyano‐vinylene‐linked 2D‐CN‐PPQV1 (Eg=2.4 eV) produced by the Knoevenagel reaction and imine‐linked 2D COF analog (2D‐C=N‐PPQV1, Eg=2.3 eV), unambiguously proving the superior conjugation of the vinylene‐linked 2D CPs using the HWE reaction.

中文翻译:

通过 Horner-Wadsworth-Emmons 反应合成亚乙烯基连接的二维共轭聚合物。

在这项工作中,我们通过C 2对称 1的 Horner-Wadsworth-Emmons (HWE) 反应首次合成了亚乙烯基连接的 2D CP,即 2D 聚(亚苯基喹喔啉亚乙烯基)2D-PPQV12D-​​PPQV2 , 4-双(二乙基膦酰基甲基)苯或4,4′-双(二乙基膦酰基甲基)联苯与C 3 -对称2,3,8,9,14,15-六(4-甲酰基苯基)二喹喔啉[2,3- a :2 ',3'- c ]吩嗪作为单体。密度泛函理论 (DFT) 模拟揭示了初始可逆 C−C 单键形成对于晶体 2D CP 合成的关键作用。粉末 X 射线衍射 (PXRD) 研究和氮气吸附-解吸测量表明,形成了表面积高达 440 m 2  g -1的结晶双孔结构。更重要的是,将所获得的2D-PPQV1(E g =2.2 eV)和2D-PPQV2(E g =2.2 eV)的光电性质与氰基-亚乙烯基连接的2D-CN-PPQV1(E g =2.4 eV)由 Knoevenagel 反应和亚胺连接的 2D COF 类似物(2D-C=N-PPQV1,E g =2.3 eV)产生,明确证明了使用 HWE 反应亚乙烯基连接的 2D CP 具有优异的共轭性。
更新日期:2020-09-22
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