Printed in Great Britain. @ 1993 IUPAC Self-assem bly and macromolecular design

Abstract- The viability of self-assembly as a new concept for the synthesis of novel materials is being vindicated by the creation of increasingly complicated molecular and supramolecular architectures. The extrapolation from alternating donor/acceptor stacks of aromatic rings in the solid state to polycatenanes, polyrotaxanes and double helices in the solution state requires the precise control of molecular recognition processes. This precision is demonstrated by the template-directed synthesis of a wide range of catenanes and rotaxanes. It emerges that, provided the building blocks contain enough molecular information to induce formation of continuously ordered stacks in the crystalline state, then it is possible to exploit this "intelligence " in the self-assembly of exotic macromolecules and polymeric supermolecules in solution