Discrete Patterned Functional Polymeric Nanostructures via Controlled Biaxial Iterative Synthesis.

Abstract

Precise sequence control in natural macromolecules underlies the structural and functional diversity that enables molecularly complex living organisms. Inspired by nature, numerous synthetic approaches have been developed for uniaxial sequence control in synthetic polymers. However, these methodologies have struggled to achieve accurate multidirectional control of the molecular structure and monomer sequence. Here, we report a robust controlled biaxial iterative synthesis (CBIS) strategy in the liquid phase, enabling atomic-precision control of biaxial chain extension. Density functional theory simulations were employed to investigate the molecular mechanisms underlying coupling reactions in both uniaxial and biaxial orientations. Using this approach, diversified patterned polymeric nanostructures (zigzag, J, T, and U motifs) were produced with atomic precision. The structural and functional complexity were introduced into discrete patterned polyporphyrins via the CBIS strategy, enabling tunable optical performance, reactive oxygen species generation, and photodynamic therapeutic efficacy, thereby highlighting their potential for applications in energy, informatics, and pharmaceuticals.