Chapter 1. Surface Self-assembly of Functional Supramolecular Networks

Abstract

Two-dimensional assembly of molecules on surfaces represents a significant challenge to chemists, materials scientists and physicists and yet offers intriguing opportunities for the development of new low-dimensional materials. The development of new materials requires efficient strategies for placing molecules in specific sequences and thus supramolecular chemistry offers many advantageous strategies for the development of such arrays. This chapter reveals how intermolecular interactions can be exploited to control molecular organisation on surfaces, demonstrating the use of hydrogen bonds, van der Waals interactions, metal–ligand coordination and covalent coupling to construct low-dimensional structures on surfaces. The chapter will emphasise the factors that affect array formation and illustrate the ability of designed arrays to entrap guest species mimicking host–guest chemistry in the solution phase. Further, the chapter will discuss how, through the use of the molecular and sub-molecular resolution of scanning probe microscopies—particularly scanning tunnelling microscopy (STM)—the precise arrangement of molecular assemblies can be probed and reveal unprecedented structural arrangements and structures. Such images provide great insight into the advantages and restrictions of working in two dimensions in comparison to the solution phase or the solid state.