Chiral Diketopyrrolopyrrole-Based Conjugated Polymers with Intramolecular Rotation-Isomeric Conformation Asymmetry for Near-Infrared Circularly Polarized Light-Sensing Organic Phototransistors.

ABSTRACT

Recent advances in chiral nanomaterials interacting with circularly polarized (CP) light open new expectations for optoelectronics in various research fields such as quantum- and biology-related technology. To fully utilize the great potential of chiral optoelectronic devices, the development of chiral optoelectronic devices that function in the near-infrared (NIR) region is required. Herein, we demonstrate a NIR-absorbing, chiroptical, low-band-gap polymer semiconductor for high-performance NIR CP light phototransistors. A newly synthesized diketopyrrolopyrrole-based donor-acceptor-type chiral π-conjugated polymer with an asymmetric alkyl side chain exhibits strong chiroptical activity in a wavelength range of 700-1000 nm. We found that the attachment of an enantiomerically pure stereogenic alkyl substituent to the π-conjugated chromophore backbone led to strong chiroptical activity through symmetry breaking of the π-conjugation of the backbone in a molecular rotational motion while maintaining the coplanar backbone conformation for efficient charge transport. The NIR CP light-sensing phototransistors based on a chiral π-conjugated polymer photoactive single channel layer exhibit a high photoresponsivity of 26 A W-1 under NIR CP light irradiation at 920 nm, leading to excellent NIR CP light distinguishability. This study will provide a rationale and strategy for designing chiral π-conjugated polymers for high-performance NIR chiral optoelectronics.