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Despite having ligands with almost identical conformations, the structures of the AgI complexes of 1 and 2 differ significantly: ligand 1 forms a double‐helical complex of P chirality, and 2 gives a triple‐helical complex (depicted on the right). The reason for the difference appears to be the existence of strong interligand stacking in the latter case.

Many and varied are the effects which control the self‐assembly of silver helicates, as illustrated schematically: besides the structure of the ligand and the coordination preferences of the metal, conditions such as the nature of the solvent and the concentration may also exert an influence.

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