Tricomponent Supramolecular Multiblock Copolymers with Tunable Composition via Sequential Seeded Growth

Synthesis of supramolecular block co-polymers (BCP) with small monomers and predictive sequence requires elegant molecular design and synthetic strategies. Herein we report the unparalleled synthesis of tri-component supramolecular BCPs with tunable microstructure by a kinetically controlled sequential seeded supramolecular polymerization of fluorescent pi-conjugated monomers. Core-substituted naphthalene diimide (cNDI) derivatives with different core substitutions and appended with beta-sheet forming peptide side chains provide perfect monomer design with spectral complementarity, pathway complexity and minimal structural mismatch to synthesize and characterize the multi-component BCPs. The distinct fluorescent nature of various cNDI monomers aids the spectroscopic probing of the seeded growth process and the microscopic visualization of resultant supramolecular BCPs using Structured Illumination Microscopy (SIM). Kinetically controlled sequential seeded supramolecular polymerization presented here is reminiscent of the multi-step synthesis of covalent BCPs via living chain polymerization. These findings provide a promising platform for constructing unique functional organic heterostructures for various optoelectronic and catalytic applications.

Automated summary

The synthesis of supramolecular block co-polymers with small monomers and predictive sequence requires elegant molecular design and synthetic strategies. A kinetically controlled sequential seeded supramolecular polymerization method was reported to synthesize tri-component supramolecular BCPs with tunable microstructure, with the use of fluorescent pi-conjugated monomers and core-substituted naphthalene diimide derivatives. This method provides a promising platform for constructing unique functional organic heterostructures for various optoelectronic and catalytic applications.