Liu Kejun, Li Jiang, Qi Haoyuan, Hambsch Mike, Rawle Jonathan, Vázquez Adrián Romaní, Nia Ali Shaygan, Pashkin Alexej, Schneider Harald, Polozij Mirosllav, Heine Thomas, Helm Manfred, Mannsfeld Stefan C B, Kaiser Ute, Dong Renhao, Feng Xinliang
Faculty of Chemistry and Food Chemistry & Center for Advancing Electronics Dresden, Technische Universität Dresden, 01062, Dresden, Germany.
Leibniz-Institut für Polymerforschung Dresden e.V. (IPF), 01069, Dresden, Germany.
Angew Chem Int Ed Engl. 2021 Jun 14;60(25):13859-13864. doi: 10.1002/anie.202102984. Epub 2021 May 11.
Two-dimensional polymers (2DPs) are a class of atomically/molecularly thin crystalline organic 2D materials. They are intriguing candidates for the development of unprecedented organic-inorganic 2D van der Waals heterostructures (vdWHs) with exotic physicochemical properties. In this work, we demonstrate the on-water surface synthesis of large-area (cm ), monolayer 2D polyimide (2DPI) with 3.1-nm lattice. Such 2DPI comprises metal-free porphyrin and perylene units linked by imide bonds. We further achieve a scalable synthesis of 2DPI-graphene (2DPI-G) vdWHs via a face-to-face co-assembly of graphene and 2DPI on the water surface. Remarkably, femtosecond transient absorption spectroscopy reveals an ultra-fast interlayer charge transfer (ca. 60 fs) in the resultant 2DPI-G vdWH upon protonation by acid, which is equivalent to that of the fastest reports among inorganic 2D vdWHs. Such large interlayer electronic coupling is ascribed to the interlayer cation-π interaction between 2DP and graphene.
二维聚合物（2DPs）是一类原子级/分子级薄的结晶有机二维材料。它们是开发具有奇异物理化学性质的前所未有的有机-无机二维范德华异质结构（vdWHs）的有趣候选材料。在这项工作中，我们展示了在水表面合成大面积（厘米级）、具有3.1纳米晶格的单层二维聚酰亚胺（2DPI）。这种2DPI由通过酰亚胺键连接的无金属卟啉和苝单元组成。我们还通过在水表面将石墨烯和2DPI面对面共组装，实现了2DPI-石墨烯（2DPI-G）vdWHs的可扩展合成。值得注意的是，飞秒瞬态吸收光谱揭示了在所得的2DPI-G vdWH中，经酸质子化后存在超快的层间电荷转移（约60飞秒），这与无机二维vdWHs中最快的报道相当。这种大的层间电子耦合归因于2DP与石墨烯之间的层间阳离子-π相互作用。
