Modulating the Chiroptical Response of Chiral Polymers with Extended Conjugation within the Structural Building Blocks.

Advancing the emerging area of chiral photonics requires modeling-guided concepts of chiral material design to enhance optical activity and associated optical rotatory dispersion. Herein, we introduce conformational engineering achieved by tuning polymer backbone conjugation through introduction of thiophene structural units in a chiral fluorene polymer backbone. Our theoretical calculations reveal a relationship between the structural conformation and the resultant rotational strength. We further synthesize a series of chiral fluorene-based polymers copolymerized with thiophene whose optical chirality trend is in qualitative agreement with predictions of our quantum chemical calculations. Varying the number of thiophene units in the monomer building block allows us to modulate the rotational strength by tuning the intrafibril helicity of single-stranded polymer chains, whereby the monomer conjugation is retained throughout the whole length of the polymer backbone. Our design concept delineates an underexamined approach: the concept of tuning backbone conjugation and helicity within the main chain to enhance the optical activity of chiral polymer systems.