On-surface molecular nanoarchitectonics: From self-assembly to directed assembly

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<jats:title>Abstract</jats:title> <jats:p>The rogress of on-surface molecular nanoarchitectonics over the last two decades has been reviewed. Over the early period in the 1990s–2000s, molecular self-assemblies were intensively studied, where van der Waals (vdW) interaction was predominant. After that, in the 2000s, selective intermolecular interactions based on hydrogen bonds and metal–molecule coordination enabled one to direct the assembling behaviors. Here, the concept of this directed assembly is opposite to that of the vdW-based self-assembly because the resulting architectures are purposefully tailored by programing intermolecular interaction. These efforts brought forth fruit in the on-surface syntheses of covalent bond networks. Particularly in the 2010s, on-surface covalent coupling was applied to graphene nanoribbons, where widths and edge structures can be precisely defined on the atomic scale. These works have the potential to bridge fundamental material nanoarchitectonics and functional device fabrication. In this paper, such a historical development of on-surface molecular nanoarchitectonics is reviewed, with the specific emphasis on the superiority of scanning tunneling microscopy.</jats:p>

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