Supramolecular Nanostructuring of Silver Surfaces via Self‐Assembly of [60]Fullerene and Porphyrin Modules

Abstract

Recent achievements in our laboratory toward the “bottom‐up” fabrication of addressable multicomponent molecular entities obtained by self‐assembly of C60 and porphyrins on Ag(100) and Ag(111) surfaces are described. Scanning tunneling microscopy (STM) studies on ad‐layers constituting monomeric and triply linked porphyrin modules showed that the molecules self‐organize into ordered supramolecular assemblies, the ordering of which is controlled by the porphyrin chemical structure, the metal substrate, and the surface coverage. Specifically, the successful preparation of unprecedented two‐dimensional porphyrin‐based assemblies featuring regular pores on Ag(111) surfaces has been achieved. Subsequent co‐deposition of C60 molecules on top of the porphyrin monolayers results in selective self‐organization into ordered molecular hybrid bilayers, the organization of which is driven by both fullerene coverage and porphyrin structure. In all‐ordered fullerene–porphyrin assemblies, the C60 guests organize, unusually, into long chains and/or two‐dimensional arrays. Furthermore, sublimation of C60 on top of the porous porphyrin network reveals the selective long‐range inclusion of the fullerene guests within the hosting cavities. The observed mode of the C60 self‐assembly originates from a delicate equilibrium between substrate–molecule and molecule–molecule interactions involving charge‐transfer processes and conformational reorganizations as a consequence of the structural adaptation of the fullerene–porphyrin bilayer.

Two-Dimensional Nanotemplates as Surface Cues for the Controlled Assembly of Organic Molecules

“…Porphyrins are a class of molecules that can be used to construct 2D supramolecular porous networks [84]. In particular, bis(3-cyano-phenyl)-substituted porphyrins were throughly investigated on Ag(100) and Ag(111) surfaces in UHV (see Fig.…”

“…The same network on the same surface was used as a host for C 84 , a molecule 10% larger than C 60 [70]. The pores are able to accommodate clusters made up of a number of C 84 molecules ranging from 2 to 7, depending on the coverage.…”

Conjugation and optoelectronic properties of acetylenic scaffolds and charge-transfer chromophores

“…Pushing the limits in size and complexity of functional carbon-rich systems will continue to be at the center of our program in acetylene chemistry. Investigations of the larger, carbon-rich systems at the level of single molecules and their potential to form nanopatterned functional surfaces are just at the beginning [99].…”

Structure and function revealed with submolecular resolution at the liquid–solid interface

“…During recent years a variety of porous self-assembled monolayers have been created and imaged with STM, but in most cases under ultrahigh vacuum conditions. [28][29][30] A pioneering example of such a network, which is formed both under UHV and at liquid-solid interfaces, is based on the trimesic acid TMA building block (see Fig. 3).…”