Supramolecular self-assembly by layering orthogonality to program identity, connectivity and conformation

Area of Science:

• Supramolecular Chemistry
• Materials Science
• Organic Chemistry

Background:

• Supramolecular systems self-assemble via reversible interactions, forming defined architectures.
• Natural systems like enzymes and membranes demonstrate parallel control of component assembly through dynamic interactions.
• Replicating this control in artificial systems is key for advanced molecular engineering.

Purpose of the Study:

• To review strategies for programming artificial supramolecular assembly using various reversible interactions.
• To highlight the use of diverse non-covalent and dynamic-covalent bonds for precise structural control.
• To showcase the construction of complex, low-symmetry, and topologically intricate supramolecular architectures.

Main Methods:

• Utilizing dynamic-covalent bonds for reversible network formation.
• Employing metal-coordination interactions to direct assembly.
• Leveraging hydrogen bonding, σ-hole, and π-interactions for specific molecular recognition and organization.

Main Results:

• Demonstrated the independent and concerted use of multiple reversible interactions to program supramolecular assembly.
• Showcased the creation of discrete receptors, capsules, cages, and interlocked architectures with high structural precision.
• Highlighted the successful design of complex foldamers and low-symmetry systems through equilibrium control.

Conclusions:

• Diverse reversible interactions can be individually or combined to precisely program the self-assembly of sophisticated supramolecular structures.
• This approach allows for the rational design of complex architectures, including those with low symmetry and intricate topologies.
• The findings provide a framework for advancing the design of artificial systems that mimic the functional complexity of natural supramolecular assemblies.