Revealing the Orientation Selectivity of Tetrapyridyl-Substituted Porphyrins Constrained in Molecular "Klotski Puzzles".

Abstract

Understanding and controlling molecular orientations in self-assembled organic nanostructures are crucial to the development of advanced functional nanodevices. Scanning tunneling microscopy (STM) provides a powerful toolbox to recognize molecular orientations and to induce orientation changes on surfaces at the single-molecule level. Enormous effort has been devoted to directly controlling the molecular orientations of isolated single molecules in free space. However, revealing and further controlling molecular orientation selectivity in constrained environments remain elusive. In this study, by a combination of STM imaging/manipulations and density functional theory calculations, we report the orientation selectivity of tetrapyridyl-substituted porphyrins in response to various local molecular environments in artificially constructed molecular "Klotski puzzles" on Au(111). With the assistance of STM lateral manipulations, "sliding-block" molecules were able to enter predefined positions, and specific molecular orientations were adopted to fit the local molecular environments, in which the intermolecular interaction was revealed to be the key to achieving the eventual molecular orientation selectivity. Our results demonstrate the essential role of local molecular environments in directing single-molecule orientations, which would shed light on the design of molecular structures to control preferred orientations for further applications in molecular nanodevices.