Inducing a chiral twist in achiral porphyrins: tailoring molecular interactions for circularly polarized luminescence from chiral microflowers.

Circularly polarized luminescent (CPL) materials are gaining prominence in next-generation optoelectronic technologies, including 3D displays, optical data storage, smart sensors and chiroptical light sources for asymmetric synthesis. The inherent limitations associated with tedious synthetic protocols has limited the use of a wide variety of organic systems as CPL emitters. In this work, we report a novel and facile strategy to achieve chiral light emission from achiral porphyrin supramolecular assemblies, thereby overcoming the inherent challenges associated with the use of this class of molecules in CPL investigations. A series of porphyrin derivatives appended with four dipicolylamine units, in the presence of l/d-mandelic acid and zinc(ii) ions, formed supramolecular aggregates exhibiting chiroptical responses. The porphyrin undergoes self-assembly following an isodesmic model of polymerization, resulting in uniform chiral microflowers exhibiting high CPL activity. Systematic investigations on the specific interactions at the molecular level helped probe the mechanism of ground and excited-state optical activity. Notably, when incorporated in polymeric films, the self-assembled structures retained their CPL activity, showcasing the potential application of the microflowers as chiral light emitting materials. The fundamental molecular understanding of chiral induction in achiral porphyrin derivatives paves the way for the development of CPL-active materials across a broader range of organic fluorophores.