Strict self-assembly of polymetallic helicates: the concepts behind the semantics

The theoretical and rational modelling of self-assembly processes is far less developed than the flourishing structural characterization of the resulting sophisticated and aesthetically appealing polymetallic architectures. However, an eventual predictive design based on molecular programming requires a detailed understanding of the chemical and physical concepts controlling self-assembly. Although the kinetic and thermodynamic background of multicomponent complexation processes remain suspicious to synthetic chemists, the recent development of two simple and complementary models for rationalizing the formation of polymetallic helicates opens the possibility of reliable predictions for the properties of multimetallic one-dimensional oligomers. The origin, theoretical base, and application of this approach for the modelling of helicates is discussed, together with its limitations and extensions toward multi-dimensional complexes.