Hydrogen-bonded π-conjugated supramolecular polymers

Abstract

The self-assembly of π-conjugated molecules offers a promising route for designing advanced functional materials with tailored optical and electronic properties. Owing to their nature, organic π-conjugated scaffolds spontaneously assemble by π–π stacking, while the introduction of hydrogen-bonding (H-bonding) interactions in these systems has emerged as a key strategy to gain control over self-assembly processes and the resulting supramolecular assemblies. H-bonding provides both specificity and directionality in non-covalent interactions, facilitating the formation of well-ordered and stable structures, such as supramolecular polymers. This review examines recent advances in design strategies that leverage H-bonding chromophores to fine-tune self-assembly behavior in solution, discussing the impact of monomer design and the experimental conditions on molecular packing and the morphologies of the resulting assemblies. Along with the thermodynamic advantages of H-bonding, its impact on self-assembly kinetics is also discussed, highlighting phenomena such as pathway complexity and related concepts like living supramolecular polymerization, secondary nucleation and supramolecular polymorphism. By providing a comprehensive overview of the current state of the field, this work aims to guide future research efforts toward the rational design of hierarchically ordered π-conjugated supramolecular materials.