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

Abstract

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.

Micrometre-long covalent organic fibres by photoinitiated chain-growth radical polymerization on an alkali-halide surface

“…In this solvent-free environment, classical chemical reactions such as Ullmann type coupling, 7,8,9,10,11,12 Glaser coupling, 13,14 imine formation, 15 self-condensation of boronic acids, 16,17,18 and many more (for overviews see refs. 19,20,6,21,22,23 ) have successfully been used to create well-defined and covalently bound organic 1D and 2D structures. Key factors for this success are first the confinement to 2D and the adsorption on a well-chosen surface that can favour both thermodynamic and kinetic progression of the polymerization process.…”

Self-assembly as a key player for materials nanoarchitectonics

“…Although nanoarchitectonics contains several different approaches for its construction mechanisms, self-assembling processes are often crucial involving a wide range of component materials. Therefore, an overview of emerging examples of self-assembling processes is meaningful in a re-examination of the recent progress in materials' nanoarchitectonics [101][102][103][104][105]. Previously, in 2008, we published a comprehensive review titled 'Challenges and Breakthroughs in Recent Research on Self-Assembly' [106].…”

Materials informatics for self-assembly of functionalized organic precursors on metal surfaces

“…While the importance of hydrogen bonding for forming 2D tilings in is well-known 1 , 2 , 14 – 18 , the other connections between functional group properties and island shape elucidated above appear new and may be helpful for bottom-up fabrication of low-dimensional nanomaterials from functionalized bianthracene precursors on Cu(111). We stress that the dendrogram is only intended to connect island shapes with functional group properties, and is not meant to identify the physical mechanisms that lead to a particular island shape.…”

“…Bottom-up fabrication, which refers to the spontaneous formation of new materials via self-assembly of molecule precursors, is a way to create low-dimensional nanomaterials with atomic-scale structural precision 1 , 2 . In order to successfully assemble a specific nanomaterial via bottom-up fabrication, precursor molecules that interact and align correctly with each other during the self-assembly process must be first identified.…”