Reactivity in organised assemblies

Abstract

This article discusses recent publications on chemical reactivity in large organic structures, including supramolecular systems (e.g., host-guest complexes), dendrimers, colloids (e.g., micelles, vesicles, microemulsions), nanoparticles and thin films. Although these systems are very different structurally, the main factors affecting organic reactivity in these assemblies are similar. These effects are: (i) proximity of functional groups in organised assemblies that may facilitate reactions between them (''proximity effect''); (ii) partitioning of the reagents between the bulk solvent and the organised assembly, which determines the local concentration of reagents in the vicinity of the functional group (''solvent effect''); (iii) unique properties of the interface between the organic assembly and the bulk solution (''interface effect''); (iv) restricted and/or anisotropic mobility of organic molecules in the organised assembly (''steric effect''). This article aims to describe each effect using examples from different types of organic assemblies. The review covers literature published in 2006 and early 2007.

Reactivity in organised assemblies

“…À by 3-alkylpolyhydroxyflavones (FnH) [eqn (2)] with alkyl chains of n = 1, 4, 6, 10 carbons was studied 10 in cetyltrimethylammonium bromide (CTAB) and non-ionic (Triton X100) micellar solutions buffered at pH 7. In the micellar pseudophase the reaction is likely to occur in the Stern layer.…”

“…We have chosen to interpret ''organised assemblies'' in a rather more liberal way than in previous years. [1][2][3] now including assemblies such as those involving DNA as well as constructions resulting from dynamic combinatorial self assembly which were turned into covalent ''non dynamic assemblies''. In all cases, however, (self) organisation and (self) assembly are crucial to the results discussed.…”

Organized molecular systems as reaction media

“…Organic chemistry has now developed so far that it is time to ask organic chemists about the future of their discipline, and reactivity in organized assemblies is one of the answers to this question [9]. A variety of synthetic reactions have been performed in organized molecular systems (OMS) formed by aggregations of individual molecules [10].…”