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Molecular self-assembly is a strategy for nanofabrication that involves designing molecules and supramolecular entities so that shape-complementarity causes them to aggregate into desired structures. Self-assembly has a number of advantages as a strategy: first, it carries out many of the most difficult steps in nanofabrication -- those involving atomic-level modification of structure -- using the very highly developed techniques of synthetic chemistry. Second, it draws from the enormous wealth of examples in biology for inspiration: self-assembly is one of the most important strategies used in biology for the development of complex, functional structures. Third, it can incorporate biological structures directly as components in the final systems. Fourth, because it requires that the target structures be the thermodynamically most stable ones open to the system, it tends to produce structures that are relatively defect-free and self-healing. Self-assembly also poses a number of substantial intellectual challenges. The brief summary of these challenges is that we do not yet know how to do it, and cannot even mimic those processes known to occur in biological systems at other than quite elementary levels. In addition, there are issues of function in self-assembled aggregates that need solution. The most promising avenues for self-assembly are presently those based on organic compounds, and organic compounds, as a group (although with exceptions), are electrical insulators; thus, many ideas for information processing and electrical/mechanical transduction will require either fundamental redesign in going from the macroscopic systems presently used to self-assembled systems, or the development of new types of organic molecules that show appropriate properties. This talk outlines some of these issues, and illustrates one of the approaches to self-assembled structures that has been particularly successful: that is, self- assembly on surfaces. There are now a range of different molecular systems that self-assemble -- that is, form ordered, monomolecular structures -- by the coordination of molecules to surfaces. These systems -- self-assembled monomlayers (SAMs) -- are reasonably well understood, and increasingly useful technologically. The crucial dimension in SAMs is the thickness perpendicular to the plane of the monolayer: this dimension, and the composition along this axis, can be controlled very simply at the scale of 0.1 nm by controlling the structures of the molecules making up the monolayer. (truncated)
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