Quantitative Measurement of Magnetic Hyperfine Parameters and the Physical Organic Chemistry of Supramolecular Systems

Abstract

The physical principles that underlie organic reactions were established by a systematic study of chemical reaction dynamics that employed correlated measurements of reaction rates and a physical parameter that could be related of the electronic properties of the molecules in question (Hammett, 1970). Today, molecular science emphasizes the concept of molecular device, which connotes a supramolecular structure (the term “supramolecule” loosely means a molecule that has multiple functionalities associated with it; for example, an enzyme might be regarded as a supramolecule in the sense that it features a supported metal catalyst and a receptor site that recognizes a specific substrate upon which the catalyst acts) that acts in some specific fashion. A molecular device may be biological (e.g., enzymes, contractile proteins; cf. Tanford & Reynolds, 2001), or it may be produced by synthetic means (e.g., molecular wires, switches, machines, etc.; cf. Sauvage, 2001; Balzani et al., 2003). Current synthetic chemistry provides the technical means that enable one to create and modify molecular devices so that structure may elicit some specific function, and so physical organic chemists are interested in reactions that involve engineered and structurally complex systems such as supported catalysts, protein active sites, or nanostructures (cf. amilton, 1996; Tidwell et al., 1997).