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.
| Identifer | oai:union.ndltd.org:DRESDEN/oai:qucosa:de:qucosa:90949 |
| Date | 21 May 2024 |
| Creators | Pastoetter, Dominik L., Xu, Shunqi, Borrelli, Mino, Addicoat, Matthew, Biswal, Bishnu P., Paasch, Silvia, Dianat, Arezoo, Thomas, Heidi, Berger, Reinhard, Reineke, Sebastian, Brunner, Eike, Cuniberti, Gianaurelio, Richter, Marcus, Feng, Xinliang |
| Publisher | Wiley-VCH |
| Source Sets | Hochschulschriftenserver (HSSS) der SLUB Dresden |
| Language | English |
| Detected Language | English |
| Type | info:eu-repo/semantics/publishedVersion, doc-type:article, info:eu-repo/semantics/article, doc-type:Text |
| Rights | info:eu-repo/semantics/openAccess |
| Relation | 1433-7851, 10.1002/anie.202010398, info:eu-repo/grantAgreement/European Commission/H2020 | SGA-RIA/881603//GrapheneCore3/Graphene Flagship Core Project 3, info:eu-repo/grantAgreement/Deutsche Forschungsgemeinschaft/SFB 1415/417590517//Chemistry of Synthetic Two-Dimensional Materials, info:eu-repo/grantAgreement/European Commission/H2020 | ERC | ERC-COG/819698//Development of Thiophene Based Conjugated Polymers in Two Dimensions/T2DCP, info:eu-repo/grantAgreement/European Commission/H2020|MSCA-ITN/813036//Bottom-Up generation of atomicalLy precise syntheTIc 2D MATerials for high performance in energy and Electronic applications – A multi-site innovative training action/ ULTIMATE |
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