Synthesis of Complex Molecular Systems—The Foreseen Role of Organic Chemists

Abstract

How to control the self-assembly of complex molecular systems is unknown. Yet, these complex molecular systems are fundamental for advances in material and biomedical sciences. A step forward is to transform one-step self-assembly into multistep synthesis involving covalent and noncovalent reactions. Key to this approach is to explore the chemical space at the frontiers of advanced covalent synthesis and supramolecular chemistry. Herein, we describe a selection of such reported cases and provide a guide for current limitations and insights for future directions. This outlook is meant to trigger collaborations between synthetic organic and supramolecular chemists, to expand the repertoire of organic syntheses working with supramolecular assemblies and thereby join forces to achieve stepwise emergence of molecular complexity in supramolecular systems.

Stereoselective Primary and Secondary Nucleation Events in Multicomponent Seeded Supramolecular Polymerization

“…Supramolecular polymers formed by the noncovalent association of monomers have evolved over the last three decades as the most promising candidates for the design of dynamic, adaptive, and recyclable materials . Control of molecular self-assembly at all length scales and at various hierarchical levels is important for the precision synthesis of supramolecular polymers.…”

A Highly Entangled (M3L2)8 Truncated Cube from the Anion-Controlled Oligomerization of a π-Coordinated M3L2 Subunit

“…The obtained results encouraged us to generalize this strategy to achieve larger nanostructures with higher structural complexity. 19 Furthermore, as 5 contains a considerably expanded spherical void space (diameter: ∼1 nm) in comparison to the lower oligomeric cages in this series, we plan to focus on cavity functionalization and guest encapsulation in future studies.…”

“…The structural characterization of 5 provided an integral understanding of the complicated structures of the series of (M 3 L 2 ) n polyhedral cages, which combine two-layered helical tripods (M 3 L 2 ) and twisted double lines. The obtained results encouraged us to generalize this strategy to achieve larger nanostructures with higher structural complexity . Furthermore, as 5 contains a considerably expanded spherical void space (diameter: ∼1 nm) in comparison to the lower oligomeric cages in this series, we plan to focus on cavity functionalization and guest encapsulation in future studies.…”

Selection between Competing Self-Reproducing Lipids: Succession and Dynamic Activation

“…This work suggests that increased species diversity can unlock new pathways in evolving systems and uncovered a dynamic activation mechanism that may be strategically useful in small molecule and supramolecular synthesis. 59 , 60 …”