Manipulating the Chiral Self‐Assembly of Achiral Porphyrin Molecules with Carbon Nanotubes as Templates

Abstract The chiral self‐assembly of achiral molecules has sparked significant interest because of its capacity to transcend the intrinsic properties of achiral monomers while eliciting emergent chiral characteristics and applications. Herein, the study presents a systematic investigation of achiral tetraphenyl porphyrin (TPP) self‐assembly utilizing chirality‐sorted achiral (10,0) single‐wall carbon nanotubes (SWCNTs) as structuring templates. Comprehensive characterization through optical absorption and photoluminescence spectroscopies confirms the effective stacking of non‐water‐soluble TPP molecules onto nanotube surfaces within surfactant‐stabilized aqueous media, achieved through optimized ultrasonication and centrifugation processes. Notably, a robust bisignate circular dichroism signal is detected for the stacked TPPs, providing definitive spectroscopic evidence of the chiral self‐assembly of inherently achiral TPP molecules into optically active helical architectures on SWCNT templates. Furthermore, the current chiral self‐assembly of TPP molecules driven by strong π–stacking interactions with SWCNTs is further verified to exhibit reversible thermodynamic behaviour, which can be precisely manipulated through the TPP/SWCNT concentration ratio and environmental temperature. The findings establish a versatile platform consisting of 1D SWCNT templates for inducing and manipulating chirality in achiral molecular systems and provide fundamental insights critical for advancing chiral recognition/sensing technologies and enantioselective catalysis applications.