Perspectives in Supramolecular Chemistry—From Molecular Recognition towards Molecular Information Processing and Self‐Organization

Abstract

The selective binding of a substrate by a molecular receptor to form a supramolecular species involves molecular recognition which rests on the molecular information stored in the interacting species. The functions of supermolecules cover recognition, as well as catalysis and transport. In combination with polymolecular organization, they open ways towards molecular and supramolecular devices for information processing and signal generation. The development of such devices requires the design of molecular components performing a given function (e.g., photoactive, electroactive, ionoactive, thermoactive, or chemoactive) and suitable for assembly into an organized array. Light‐conversion devices and charge‐separation centers have been realized with photoactive cryptates formed by receptors containing photosensitive groups. Eleclroactive and ionoactive devices are required for carrying information via electronic and ionic signals. Redox‐active polyolefinic chains, like the “caroviologens”, represent molecular wires for electron transfer through membranes. Push‐pull polyolefins possess marked nonlinear optical properties. Tubular mesophases, formed by organized stacking of suitable macro‐cyclic components, as well as “chundle”‐type structures, based on bundles of chains grafted onto a macrocyclic support, represent approaches to ion channels. Lipophilic macrocyclic units form Langmuir‐Blodgett films that may display molecular recognition at the air‐water interface. Supramolecular chemistry has relied on more or less preorganized molecular receptors for effecting molecular recognition, catalysis, and transport processes. A step beyond preorganization consists in the design of systems undergoing self‐organization, that is, systems capable of spontaneously generating a well‐defined supramolecular architecture by self‐assembling from their components under a given set of conditions. Several approaches to self‐assembling systems have been pursued: the formation of helical metal complexes, the double‐stranded helicates, which result from the spontaneous organization of two linear polybipyridine ligands into a double helix by binding of specific metal ions; the generation of mesophases and liquid crystalline polymers of supramolecular nature from complementary components, amounting to macroscopic expression of molecular recognition; the molecular‐recognition‐directed formation of ordered solid‐state structures. Endowing photo‐, electro‐, and ionoactive components with recognition elements opens perspectives towards the design of programmed molecular and supramolecular systems capable of self‐assembly into organized and functional supramolecular devices. Such systems may be able to perform highly selective operations of recognition, reaction, transfer, and structure generation for signal and information processing at the molecular and supramolecular levels.