Near-Ultraviolet Circular Dichroism of Achiral Phenolic Termini Induced by Nonchromophoric Poly(l,l-lactide) and Poly(d,d-lactide).

Abstract

Herein, we present the first induced chirality of vanillin and its phenolic analogs attached to the chain ends of poly(l,l-lactide) and poly(d,d-lactide). Vanillin analogs were used as chromophoric and luminophoric, but achiral, ring-opening initiators of corresponding chiral cyclic lactides. Induced chirality was evident from clear circular dichroism bands at 270-320 nm due to π-π* and n-π* transitions at the vanillin moiety. However, no circularly polarized luminescence band was detected. Density functional theory (DFT) and time-dependent DFT calculations suggested the existence of multiple through-space intramolecular CH/O interactions between the ortho-methoxy moiety of vanillin and nearest-neighbor lactic acid units. The terminus sensitively indicated whether the main-chain chirality was l or d.