Synthesis of Vinylene-Linked Two-Dimensional Conjugated Polymers via the Horner-Wadsworth-Emmons Reaction

被引：122

作者：

Pastoetter, Dominik L. ^{[1
,2
]}

Xu, Shunqi ^{[1
,2
]}

Borrelli, Mino ^{[1
,2
]}

Addicoat, Matthew ^{[3
]}

Biswal, Bishnu P. ^{[4
]}

Paasch, Silvia ^{[5
]}

Dianat, Arezoo ^{[6
]}

Thomas, Heidi ^{[7
]}

Berger, Reinhard ^{[1
,2
]}

Reineke, Sebastian ^{[7
]}

Brunner, Eike ^{[5
]}

Cuniberti, Gianaurelio ^{[6
]}

Richter, Marcus ^{[1
,2
]}

Feng, Xinliang ^{[1
,2
]}

机构：

[1] Tech Univ Dresden, Chair Mol Funct Mat, Ctr Adv Elect Dresden Cfaed, D-01062 Dresden, Germany

[2] Tech Univ Dresden, Fac Chem & Food Chem, D-01062 Dresden, Germany

[3] Nottingham Trent Univ, Sch Sci & Technol, Nottingham NG1 18NS, England

[4] Ashoka Univ Rajiv Gandhi Educ City, Dept Chem, Sonipat Delhi Ncr 131029, Haryana, India

[5] Tech Univ Dresden, Fac Chem & Food Chem, Chair Bioanalyt Chem, D-01062 Dresden, Germany

[6] Tech Univ Dresden, Fac Mech Sci & Engn, Chair Mat Sci & Nanotechnol, D-01062 Dresden, Germany

[7] Tech Univ Dresden, Dresden Integrated Ctr Appl Phys & Photon Mat IAP, D-01187 Dresden, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2020年 / 59卷 / 52期

基金：

欧盟地平线“2020”;

关键词：

2D conjugated polymers; 2D covalent organic frameworks; 2D materials; Horner-Wadsworth-Emmons reaction; vinylene-linked; ELECTRONIC-PROPERTIES; CARBON;

D O I：

10.1002/anie.202010398

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

In this work, we demonstrate the first synthesis of vinylene-linked 2D CPs, namely, 2D poly(phenylenequinoxalinevinylene)s2D-PPQV1and2D-PPQV2, via the Horner-Wadsworth-Emmons (HWE) reaction ofC(2)-symmetric 1,4-bis(diethylphosphonomethyl)benzene or 4,4 '-bis(diethylphosphonomethyl)biphenyl withC(3)-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 m(2) g(-1). More importantly, the optoelectronic properties of the obtained2D-PPQV1(E-g=2.2 eV) and2D-PPQV2(E-g=2.2 eV) are compared with those of cyano-vinylene-linked2D-CN-PPQV1(E-g=2.4 eV) produced by the Knoevenagel reaction and imine-linked 2D COF analog (2D-C=N-PPQV1, E-g=2.3 eV), unambiguously proving the superior conjugation of the vinylene-linked 2D CPs using the HWE reaction.

引用

页码：23620 / 23625

页数：6

共 44 条

[41] Structure-Thermodynamic-Property Relationships in Cyanovinyl-Based Microporous Polymer Networks for the Future Design of Advanced Carbon Capture Materials [J].