Abstract

A general discussion of the routes to chemisorbed monolayers on different surfaces and under different conditions is presented, with an emphasis on the compatibility between adsorbate and adsorbent. The dominance of reports on self-assembled monolayers on gold and silicon oxide means that they are discussed most because of the greater understanding and general applicability of these systems. The characteristics of the monolayers that are formed are shown, with a critical analysis of the strengths and weaknesses of each particular system. The ways these systems can be used to generate specific structures on surfaces, and be used in binding to them, will be presented. In particular, the use of electrochemical techniques and surface plasmon resonance to probe host–guest interactions are areas where much has been done. On the other hand, chemisorbed structures on single crystal metals such as copper reveal how both adsorption conformation and footprint on the surface are critical points to be taken into account in the adsorption of organic molecules onto surfaces, as this factor ultimately affects the supramolecular chemistry taking place. Surface reconstruction must be considered in the design of supramolecular systems on metal surfaces. The robustness of many of the systems means that they can be exploited to study supramolecular chemistry in many environments, and some of these uses will be discussed.

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