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介观有序二维聚合物的表面光聚合
作者:小柯机器人 发布时间:2021/6/6 14:17:26

德国慕尼黑工业大学Markus Lackinger团队报道介观有序二维聚合物的表面光聚合策略。相关研究成果发表在2021年6月3日出版的《自然—化学》。

利用固体载体和超高真空条件合成二维聚合物,可以实现彻底的表征,通常具有亚分子分辨率,并防止污染,因此具有很强吸引力。然而,大多数表面聚合是热激活的,这通常导致高缺陷密度和相对较小的畴尺寸。

该文中,研究人员在超高真空条件下,在烷烃钝化石墨表面,通过氟化蒽三联烯(fantrip)单体的两步拓扑化学光聚合得到一种介观尺度上有序排列的多孔二维聚合物。首先,fantrip单体自组装成高度有序的单层结构,其中所有蒽部分采用适当的排列进行光聚合。紫外光照射后,通过[4+4]光环加成反应诱导完全共价交联,形成二维聚合物,同时完全保持自组装结构的长程有序性。局部红外光谱和扫描隧道显微镜表征证实了聚合程度,与密度泛函理论计算结果一致,同时给出了机理上的见解。

附:英文原文

Title: On-surface photopolymerization of two-dimensional polymers ordered on the mesoscale

Author: Lukas Grossmann, Benjamin T. King, Stefan Reichlmaier, Nicolai Hartmann, Johanna Rosen, Wolfgang M. Heckl, Jonas Bjrk, Markus Lackinger

Issue&Volume: 2021-06-03

Abstract: The use of solid supports and ultra-high vacuum conditions for the synthesis of two-dimensional polymers is attractive, as it can enable thorough characterization, often with submolecular resolution, and prevent contamination. However, most on-surface polymerizations are thermally activated, which often leads to high defect densities and relatively small domain sizes. Here, we have obtained a porous two-dimensional polymer that is ordered on the mesoscale by the two-staged topochemical photopolymerization of fluorinated anthracene triptycene (fantrip) monomers on alkane-passivated graphite surfaces under ultra-high vacuum. First, the fantrip monomers self-assemble into highly ordered monolayer structures, where all anthracene moieties adopt a suitable arrangement for photopolymerization. Irradiation with violet light then induces complete covalent crosslinking by [4+4] photocycloaddition to form a two-dimensional polymer, while fully preserving the long-range order of the self-assembled structure. The extent of the polymerization is confirmed by local infrared spectroscopy and scanning tunnelling microscopy characterization, in agreement with density functional theory calculations, which also gives mechanistic insights.

DOI: 10.1038/s41557-021-00709-y

Source: https://www.nature.com/articles/s41557-021-00709-y

期刊信息

Nature Chemistry:《自然—化学》,创刊于2009年。隶属于施普林格·自然出版集团,最新IF:21.687
官方网址:https://www.nature.com/nchem/
投稿链接:https://mts-nchem.nature.com/cgi-bin/main.plex