Hydrogen-Bonded Macrocyclic Supramolecular Systems in Solution and on Surfaces.

Area of Science:

• Supramolecular Chemistry
• Nanotechnology
• Organic Chemistry

Background:

• Noncovalent synthesis is key for creating discrete, well-defined nanostructures.
• Cyclization into closed assemblies is a common strategy for supramolecular synthesis.
• Hydrogen-bonded systems offer precise control over self-assembly.

Purpose of the Study:

• To review the noncovalent synthesis of monocyclic hydrogen-bonded systems.
• To highlight the role of intramolecular binding in self-assembly.
• To discuss factors influencing the size and fidelity of cyclic nanostructures.

Main Methods:

• Focus on self-assembly driven by intramolecular binding events.
• Thermodynamic control for quantitative yields.
• Analysis of geometric factors (monomer structure, binding directionality).
• Consideration of structural preorganization, flexibility, and templating.

Main Results:

• Intramolecular binding favors quantitative formation of supramolecular species.
• Assembly size is dictated by monomer geometry and interaction directionality.
• High fidelity is achieved through preorganization and templating.
• Examples of cycles from dimers to hexamers are discussed.

Conclusions:

• Monocyclic hydrogen-bonded systems can be quantitatively synthesized via intramolecular binding.
• Precise control over nanostructure size and fidelity is achievable.
• This approach provides a robust method for designing discrete supramolecular assemblies.