Dynamic Borate Esterification for Evolved Supramolecular Chirality and Chiral Optics

Abstract

Topological chemical reactions in confined environments offer unique opportunities for constructing dynamically tunable crystalline materials and architecturally defined polymers. However, their potential within functional supramolecular systems and chiral materials remains largely untapped. In this work, we introduce, for the first time, a borate esterification reaction to achieve dynamic modulation of supramolecular chirality and chiroptical properties under aggregation conditions. Pyrene-phenylalanine derivatives, following functionalization with phenylboronic acid groups, coassemble with catechol-functionalized pyrene derivatives. This coassembly undergoes spontaneous and highly efficient borate esterification under ambient conditions, inducing nanoscale morphological evolution, and an inversion of supramolecular chirality. Both experimental results and DFT-based computations reveal that the supramolecular chirality inversion is primarily driven by a transition from π–π stacking to CH–π interactions between pyrene moieties. This coassembly-borate esterification process represents a powerful integration of noncovalent assembly and covalent chemistry, providing a versatile platform for the design of soft materials and chiral functional systems. Moreover, the introduction of alizarin derivatives containing catechol motifs enables the transfer of circularly polarized luminescence (CPL), resulting in tunable emission shifts from blue and cyan to red. This work broadens the functional scope of chiral luminescent materials and opens new avenues for their application.