Surface Patterning with Two-Dimensional Porphyrin Supramolecular Arrays

Abstract

Monolayer arrays of a series of meso-tetra-substituted porphyrins containing octadecyloxy and carboxyl (or pyridyl) groups were prepared on the highly oriented pyrolytic graphite surface at the liquid/solid interface. It was found by means of scanning tunneling microscopy that some porphyrins from this family assemble into various patterns. Specifically, slightly undulated rows are obtained from 5,10,15-tris(4-octadecyloxyphenyl)-20-(4-pyridyl)porphyrin. Meanwhile, rows with more pronounced kinks result from 5-(4-carboxyphenyl)-10,15,20-tris(4-octadecyloxyphenyl)porphyrin. The occurrence of the kinks is dependent on the arrangement of surrounding porphyrin molecules and is determined by intricate interplay between directional hydrogen-bonding interactions and packing forces, including molecule-molecule and molecule-substrate interactions. A double-layer structure is obtained from 5,10-bis(4-carboxyphenyl)-15,20-bis(4-octadecyloxyphenyl)porphyrin, probably through cyclic hydrogen bond formation. This work proves the concept that programmed surface patterning is possible by using porphyrins incorporating directional intermolecular interaction sites.

Supramolecular Approaches to Graphene: From Self‐Assembly to Molecule‐Assisted Liquid‐Phase Exfoliation

“…[254][255][256][257] Therefore, similar interactions are expected to take place between porphyrins and graphene. [258,259] To explore this idea, Jung and coworkers dispersed graphene in the presence of 5,10,15,20-tetraphenyl-(4,11-acetyltioundecyl-oxyphenyl)-21H,23H-porphin (TATPP; Figure 15) in NMP containing organic ammonium ions.…”

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

“…A limited number of studies has been undertaken to elucidate the supramolecular behavior of single porphyrin molecules on surfaces. [43][44][45][46] In particular, their assembly with other redox-and/or photoactive molecular species, such as fullerenes, on surfaces has not been fully investigated. [47,48] Herein, we describe the advances made in our laboratory towards the "bottom-up" fabrication of organic nanopatterned surfaces based on 2D supramolecular assemblies composed of porphyrins and C 60 on Ag(100) and Ag(111).…”

Self-Organized Monolayer ofmeso-Tetradodecylporphyrin Coordinated to Au(111)

“…7 Earlier STM investigations at the liquid/solid interface have focused on the study of meso-tetraphenylporphyrins (TPPs) on highly oriented pyrolytic graphite (HOPG). [8][9][10][11] In TPP, the phenyl groups adopt an average angle of 36°with respect to the plane of the porphyrin ring, thus forcing the central ring to lie ∼0.34 nm above the surface. 12 Alternatively, meso-tetraalkylporphyrins (TAPs) such as 5,10,15,20-meso-tetradodecylporphyrin (H 2 P, Scheme 1) suffer no such steric constraints and can lie in direct contact with the surface.…”