On-Surface Synthesis of All-cis Standing Phenanthrene Polymers upon Selective C-H Bond Activation
On-Surface Synthesis of All-cis Standing Phenanthrene Polymers upon Selective C-H Bond Activation
复制标题
选择性 C–H 键激活的全顺式菲聚合物的表面合成
DOI：
10.1021/acs.jpclett.0c01349
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发表时间：
2020-07-02
影响因子：
5.7
通讯作者：
Yu, Ping
中科院分区：
文献类型：
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作者：
Du, Qingyang;Pu, Weiwen;Yu, Ping
表面合成已成为原子级精确制造分子结构的一种强大方法，在纳米技术中具有潜在的应用。然而，合成可以从表面突出的分子结构（例如由具有直立构象的分子形成的聚合物链）具有挑战性，因为大多数表面反应产物，特别是共轭结构，更喜欢平行吸附在表面上以最大化分子-基底相互作用。她;我们展示了一种直立的菲聚合物链，其具有全顺式构型，是通过高度选择性的 C-H 活化进行表面合成而获得的。利用键分辨NC-AFM成像，充分表征了聚合物从面内构象到全顺式直立构象的反应路径，并结合第一性原理计算进一步揭示了反应机理。我们关于这种选择性脱氢诱导的直立取向聚合物链的结果将丰富表面合成新型分子结构的工具箱，并可能为设计优化前体以通过表面合成制备三维分子框架提供新的见解。
On-surface synthesis has emerged as a powerful approach to the atomically precise fabrication of molecular architectures with potential applications in nanotechnology. However, it is challenging to synthesize molecular structures that can protrude from the surface such as polymer chains forming by the molecules with upright conformations, since most of the on-surface reaction products, particularly the conjugated structures, prefer to adsorb parallel on the surface to maximize the molecule-substrate interaction. Her; we show an up-standing phenanthrene polymer chain with an all-cis configuration obtained by on-surface synthesis upon highly selective C-H activation. Using bond-resolved nc-AFM imaging, the reaction route of polymers from an in-plane to an all-cis upright conformation is fully characterized, and the reaction mechanism is further revealed in combination with first principles calculations. Our results on this selective dehydrogenation induced upright-oriented polymer chains that will enrich the toolbox for the on-surface synthesis of novel molecular structures and may provide new insights on designing optimized precursors for preparing three-dimensional molecular frameworks through on-surface synthesis.