Doublet Chirality Transfer and Reversible Helical Transition in Poly(3,5‐disubstituted phenylacetylene)s with Pyrene as a Probe Unit†

Abstract

Summary of main observation and conclusionA novel doublet chirality transfer (DCT) model was demonstrated in cis poly(3,5‐disubstituted phenylacetylene)s, i.e., S‐I, R‐I, and S‐I‐NMe. The chiral message from the stereocenter of alkylamide substituent at 3‐position induced the polyene backbone to take cis‐transoid helical conformation with a predominant screw sense. And in turn the helical backbone acted as a scaffold to orient the pyrene probes, which was linked to phenyl rings through 5‐position, to array in an asymmetric manner. A combinatory analyses of 1H NMR, Raman, FTIR, UV‐vis absorption, CD, and computer simulation suggested that the main‐chain stereostructure, solvent nature, and intramolecular hydrogen bonds played important and complex roles on DCT. High cis‐structure content and intramolecular hydrogen bonds were beneficial for the realization of DCT. Reversible helix‐helix transition was observed in S‐I by changing the nature of solvents. In DMF, S‐I adopted a relatively contracted helix, where the main chain exhibited strong optical activity, but that of pyrene was weak. In contrast, a relatively stretched helix formed in CHCl3, in which the optical activity of pyrene was much larger, whereas that of the polyene backbone was the weakest. This helix‐helix transition was attributed to the intramolecular hydrogen bonds, which was confirmed by solution‐state FTIR spectra and computer calculations.