On‐surface synthesis of cumulene‐containing polymers via two‐step dehalogenative homocoupling of dibromomethylene-functionalized tribenzoazulene

The record contains data that support our recent findings in the fabrication of cumulene containing polymers. Cumulene compounds are notoriously difficult to prepare and study because their reactivity increases dramatically with the increasing number of consecutive double bonds. In this respect, the emerging field of on‐surface synthesis provides exceptional opportunities because it relies on reactions on clean metal substrates under well‐controlled ultrahigh‐vacuum conditions. In the work we report the on‐surface synthesis of a polymer linked by cumulene‐like bonds on a Au(111) surface via sequential thermally activated dehalogenative C−C coupling of a tribenzoazulene precursor equipped with two dibromomethylene groups. The structure and electronic properties of the resulting polymer with cumulene‐like pentagon–pentagon and heptagon–heptagon connections have been investigated by means of scanning probe microscopy and spectroscopy methods and X‐ray photoelectron spectroscopy, complemented by density functional theory calculations.

本数据集收录了支撑我们近期关于含累积烯烃（cumulene）聚合物制备研究的相关实验数据。累积烯烃类化合物的合成与表征历来极具挑战性，因其反应活性随分子内连续双键数量的增加而显著提升。就此而言，新兴的表面合成（on-surface synthesis）领域提供了绝佳的研究契机，因其依托于严格可控的超高真空环境下洁净金属基底表面的反应。本研究报道了在金(111)（Au(111)）表面，通过对带有两个二溴亚甲基取代基的三苯并薁前驱体进行连续热激活脱卤C-C偶联反应，合成由类累积烯烃键连接的聚合物的表面合成过程。针对该产物中具有类累积烯烃型五边形-五边形与七边形-七边形连接结构的聚合物，我们采用扫描探针显微镜及光谱学方法、X射线光电子能谱（X-ray photoelectron spectroscopy），结合密度泛函理论（density functional theory）计算，对其微观结构与电子性质展开了系统表征与分析。