Abstract
Self-assembled monolayers (SAMs) have been the preferred material systems to investigate specific properties in several disciplines for nearly 15 years. Advances in various techniques and their application to the study of SAMs have dramatically improved our understanding of these systems. Adaptation of this molecular architecture into three dimensions in the form of monolayer-protected clusters enabled the use of bulk techniques for the study of monolayers. Here we review recent developments in the structural properties and temperature-induced phase transitions of both these SAM structures. While alkanethiols on Au (111) and Ag (111) are taken as archetypal systems to discuss the properties of SAMs on two-dimensional surfaces, their assemblies on Au and Ag cluster surfaces are taken as examples for SAMs on three-dimensional surfaces. A comparison of these two SAMs is provided.