On-surface formation of two-dimensional supramolecular network structures using molecular self-assembly has been an efficient and the most widely employed method. Through delicate modifying the molecular candidates with specific substituents, it is possible to build on-surface nanostructures according to one’s will. Here, from the interplay of high-resolution STM imaging and DFT calculations we have investigated role of the tert-butyl substituent in the formation of self-assembled network structures by planar aromatic molecules on metal surfaces. Our results demonstrate that the tert-butyl groups can change adsorption geometry of molecule from entirely flat-lying to a bit of upright-standing and vary the intermolecular interactions, which resulted in the formation of two-dimensional supramolecular network structures on both Au(111) and Ag(110). These findings further present that tert-butyl substituent could be a good candidate for fabricating on-surface self-assembled nanostructures from more general aromatic molecules.

On-surface self-assembly from molecular building blocks directed by supramolecular interactions has been widely reckoned as an efficient method for controllable construction of low-dimensional nanostructures and nanomaterials. Numerous efforts have been devoted to exploring the self-assembled behaviors of molecular precursors on different surfaces and unravelling the underlying mechanism. Generally, the molecular precursors are functionalized with one kind of functional groups for directing the self-assembly. In this study, by combining real-space direct visualization and DFT calculations, we have investigated the self-assembly behaviors of an organic molecule functionalized by two different functional groups: terminal alkyne and aldehyde groups on Au(111). An ordered racemic island nanostructure is formed on Au(111), which results from the hybrid interactions between the two functional groups. Detailed DFT calculations have been performed to compare the different binding ways and binding strengths between the organic molecules.

Molecular self-assembly is an efficient approach to fabricate supramolecular nanostructures on well-defined surfaces. The nanostructures can be regulated through functionalizing the molecular precursors with different functional groups. Here, from an interplay of high-resolution scanning tunneling microscopy imaging and density functional theory calculations, we have at the atomic scale investigated the influence of tert-butyl groups on the on-surface self-assembled behaviors of the organic molecules where intermolecular interactions mainly originate from relatively weak van der Waals interactions. Our results demonstrate that the tert-butyl groups can not only affect the adsorption geometry but also change the self-assembled properties of organic molecules on surfaces due to the enhanced intermolecular interactions.