Directed Noncovalent Synthesis of Dendritic Spherulitic Superstructures via Surface-Mediated Secondary Nucleation

The research group of Prof. Apurba Lal Koner, Department of Chemistry in collaboration with Dr. Mitradip Bhattacharjee, Department of EECS have developed supramolecular polymers with detailed insight into supramolecular polymerization via secondary nucleation and established a design principle for dynamic chiral materials with potential chiroptical sensing applications and optoelectronic devices. Unlike classical primary nucleation-elongation mechanisms, secondary nucleation has emerged as a promising route to construct advanced supramolecular polymers. Here, we demonstrate the formation of 3D dendritic spherulitic superstructures through the surface-assisted secondary nucleation-driven self-assembly of chiral perylenemonoimide dyes. Comprehensive morphological investigations reveal a well-defined hierarchical organization, culminating in the emergence of homochiral spherulites with radii reaching approximately 50 µm. Strikingly, these chiral DSS exhibit strong chiroptical properties, generating pronounced photocurrent responses under circularly polarized light, with enhanced responsivity and an average 0.33 dissymmetry factor. This breakthrough offers a robust "topological approach" to synthetic chemistry. It offers structures with programmable design of noncovalent materials. By controlling the pathway from a single molecule to a micrometer-scale 3D superstructure, we are gaining the ability to build synthetic materials with the hierarchical complexity of living tissue. As we look toward the future of molecular electronics and smart materials, a provocative question remains: "If we can now grow 3D structures on demand from a single molecule, what other biological blueprints are waiting to be replicated in the lab?" For more details, kindly visit https://onlinelibrary.wiley.com/doi/full/10.1002/smll.202513966