Calculated and structural analyses of self-assembly formed by [7]thiaheterohelicene-2,13-carboxaldehyde molecules on Au(111)

Recently, the electronic and structural properties of large self-assembled domains of [7]thiaheterohelicene-2,13-carboxaldehyde helicene ([7]TH-dial) molecules on Au(111), Cu(001), and NiAl(110) metal surfaces have been characterized by scanning tunneling microscopy (STM). Several distinct areas of the self-assembled structures can be observed. To describe and explore the morphology of and the interactions in these distinct self-assembled nanostructures, we combine the results obtained through calculations in a semi-empirical framework and calculated STM images. It is revealed that these supramolecular nanostructures, on metallic substrates, originate from the two orientations <i>P</i> and <i>M</i> of the [7]TH-dial molecules linked in different orientations (head-to-tail, sideways, head-on, and tail-on) through van der Waals interactions. The results presented here provide valuable insights for understanding the intermolecular and substrate-molecule interactions within the self-assembled nanostructures of [7]TH-dial molecules on metallic surfaces.