调整π共轭和振动模式控制并环戊二烯桥梯形聚合物的表面合成
Tailoring π-conjugation and vibrational modes to steer on-surface synthesis of pentalene-bridged ladder polymers
摘要：
π共轭聚合物的合成策略的发展在现代化学和材料科学中具有极其重要的意义。在这里，我们介绍了一个理论和实验的合成范例的基础上寻找特定的振动模式，通过适当的剪裁的π共轭的前体，以增加化学反应的尝试频率。首先，我们在表面上设计了具有特定π拓扑结构的一维π共轭聚合物，其基于通过调节特定振动模式的累积多烯桥连接的双蒽单体。在第二步骤中，在进一步退火时，这样的振动模式引导相邻的双蒽部分之间的双重环化反应，这产生了具有低带隙的长且无缺陷的并环戊二烯桥连的共轭梯形聚合物。此外，高分辨率原子力显微镜使我们能够通过原子的见解来识别聚合物的共振形式，从而证实了Glidewell和Lloyd规则的有效性。这种表面上的合成策略可以刺激利用先前被排除的反应朝向具有特定结构和性质的新型π-共轭聚合物。
英文摘要：
The development of synthetic strategies to engineer π-conjugated polymers is of paramount importance in modern chemistry and materials science. Here we introduce a theoretical and experimental synthetic paradigm based on the search for specific vibrational modes through an appropriate tailoring of the π-conjugation of the precursors, in order to increase the attempt frequency of a chemical reaction. First, we on-surface design a 1D π-conjugated polymer with specific π-topology, which is based on bisanthene monomers linked by cumulene bridges that tune specific vibrational modes. In a second step, upon further annealing, such vibrational modes steer the two-fold cyclization reaction between adjacent bisanthene moieties, which gives rise to a long and free-defect pentalene-bridged conjugated ladder polymer featuring a low band gap. In addition, high resolution atomic force microscopy allows us to identify by atomistic insights the resonant form of the polymer, thus confirming the validity of the Glidewell and Lloyd's rules for aromaticity. This on-surface synthetic strategy may stimulate exploiting previously precluded reactions towards novel pi-conjugated polymers with specific structures and properties.
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