Abstract Molecular engineering on surface has been revolutionized by the possibility to create covalent connections between molecular tectons. Following the pioneering works on supramolecular structures and their triumphal developments during a decade, covalent organic frameworks on surface open up new routes towards robust and regular porous macromolecular structures usable in practical applications such as molecular electronics, energy conversion or catalysis. Metal surfaces can be also be decorated with semiconducting organic structures, widening the scope of applicability of these polymer-modified surfaces. If the first generation of molecular building blocks was designed so that the functional groups were introduced for a specific reactivity, recently, a breakthrough has been achieved in 2016 and 2017 with the almost simultaneous reports of ENA and INDO4 capable to initiate different reaction pathways depending of the surface topography or the surface coverage. Prior to these two works, in 2015, another exciting candidate (i.e. TAPB) exhibiting however a more limited range of reactivity than ENA or INDO4 was reported, its reactivity being based on the presence of acetyl end-groups. In this minireview, the intriguing properties of these unique building blocks are presented.

中文翻译：

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二维表面共价有机框架中的分子工程：迈向下一代分子构造 - 一个小评论

摘要 由于在分子构造之间建立共价连接的可能性，表面上的分子工程已经发生了革命性的变化。继十年来超分子结构及其成功发展的开创性工作之后，表面的共价有机框架开辟了通向稳健和规则多孔大分子结构的新途径，可用于分子电子学、能量转换或催化等实际应用。金属表面也可以用半导体有机结构装饰，扩大这些聚合物改性表面的适用范围。如果第一代分子构建块的设计是为了特定的反应性而引入官能团，最近，2016 年和 2017 年取得了突破，几乎同时报告 ENA 和 INDO4 能够根据表面形貌或表面覆盖率引发不同的反应途径。在这两项工作之前，2015 年，另一个令人兴奋的候选物（即 TAPB）被报道，但其反应性范围比 ENA 或 INDO4 更有限，其反应性基于乙酰端基的存在。在这篇小评论中，介绍了这些独特构建块的有趣特性。其反应性基于乙酰基端基的存在。在这篇小评论中，介绍了这些独特构建块的有趣特性。其反应性基于乙酰基端基的存在。在这篇小评论中，介绍了这些独特构建块的有趣特性。