The supramolecular polymerization of porphyrin dyad(PD)shows the pathway complexity leading to the formation of kinetically metastable nanoparticles(PDParticle)through rapid cooling and thermodynamically stable fibrou...The supramolecular polymerization of porphyrin dyad(PD)shows the pathway complexity leading to the formation of kinetically metastable nanoparticles(PDParticle)through rapid cooling and thermodynamically stable fibrous supramolecular polymers(PDFiber)through slow cooling.The kinetically metastable PD_(Particle)is gradually transformed to the thermodynamically stable PDFiber.Due to the inherent achirality of PD,AFM images exhibited a random distribution of both M and P helices.Introducing chiral alkyl chains achieved a predominant helicity in PD_(Fiber),with(S)-PD favoring M helices and(R)-PD favoring P helices.The addition of chiral 2-methyl pyrrolidine(MePy)further influences this transformation by retarding the transition from PD_(Particle)to PD_(Fiber)through axial coordination with the zinc porphyrin units,affecting the helicity of the resulting supramolecular polymer.By manipulating the cooling rates and environmental conditions,we demonstrate the reversible control over circular dichroism(CD)and circularly polarized luminescence(CPL),providing insight into the relationship between structural chirality and optical activity.展开更多
基金supported by the National Research Foundation(NRF)grant(RS-2025-00514482,RS-2024-00345550)funded by the Ministry of Science and ICT(MSIT),Korea.
文摘The supramolecular polymerization of porphyrin dyad(PD)shows the pathway complexity leading to the formation of kinetically metastable nanoparticles(PDParticle)through rapid cooling and thermodynamically stable fibrous supramolecular polymers(PDFiber)through slow cooling.The kinetically metastable PD_(Particle)is gradually transformed to the thermodynamically stable PDFiber.Due to the inherent achirality of PD,AFM images exhibited a random distribution of both M and P helices.Introducing chiral alkyl chains achieved a predominant helicity in PD_(Fiber),with(S)-PD favoring M helices and(R)-PD favoring P helices.The addition of chiral 2-methyl pyrrolidine(MePy)further influences this transformation by retarding the transition from PD_(Particle)to PD_(Fiber)through axial coordination with the zinc porphyrin units,affecting the helicity of the resulting supramolecular polymer.By manipulating the cooling rates and environmental conditions,we demonstrate the reversible control over circular dichroism(CD)and circularly polarized luminescence(CPL),providing insight into the relationship between structural chirality and optical activity.
