π-Extended perylene diimide double-heterohelicenes as ambipolar organic semiconductors for broadband circularly polarized light detection

Abstract

Despite great challenges, the development of new molecular structures with multiple and even conflicting characteristics are eagerly pursued for exploring advanced applications. To develop high-performance chiral organic semiconducting molecules, a distorted π-system is required for strong coupling with circularly polarized light (CPL), whereas planar π-stacking systems are necessary for high charge-carrier mobility. To address this dilemma, in this work, we introduce a skeleton merging approach through distortion of a perylene diimide (PDI) core with four fused heteroaromatics to form an ortho-π-extended PDI double-[7]heterohelicene. PDI double helicene inherits a high dissymmetry factor from the helicene skeleton, and the extended π-planar system concurrently maintains a high level of charge transport properties. In addition, ortho-π-extension of the PDI skeleton brings about near-infrared (NIR) light absorption and ambipolar charge transport abilities, endowing the corresponding organic phototransistors with high photoresponsivity of 450 and 120 mA W−1 in p- and n-type modes respectively, along with a high external quantum efficiency (89%) under NIR light irradiations. Remarkably, these multiple characteristics enable high-performance broadband CPL detections up to NIR spectral region with chiral organic semiconductors.

Chiral Perylene Bisimide Dyes by Interlocked Arene Substituents in the Bay Area

“…The g lum values of around 1 ⋅ 10 −3 for the heavily twisted molecules are of typical magnitude and are comparable to those of chiral peropyrene reported by Chalifoux et al . and other chiral organic molecules [37,50–53] . The monosignated spectra of the two respective P ‐/ M ‐enantiomers are again mirror images, and the observed Stokes shifts are in accordance with the Stokes shifts obtained by UV/Vis/NIR and fluorescence measurements.…”

“…and other chiral organic molecules. [ 37 , 50 , 51 , 52 , 53 ] The monosignated spectra of the two respective P ‐/ M ‐enantiomers are again mirror images, and the observed Stokes shifts are in accordance with the Stokes shifts obtained by UV/Vis/NIR and fluorescence measurements. The sign of the CPL spectrum matches the sign of the longest wavelength transition in the CD spectrum.…”

Circularly Polarized Photodetectors Based on Chiral Materials: A Review

“…To develop high-performance chiral organic semiconducting molecules, a distorted π-system is required for strong coupling with circularly polarized light (CPL), whereas planar π-stacking systems are necessary for high charge-carrier mobility. To address this concern, Zhang et al introduced a skeleton merging approach through the distortion of a perylene diimide (PDI) core with four fused heteroaromatics to form an ortho-π-extended PDI double-[7]heterohelicene (Zhang et al, 2021). The PDI double helicene inherits high dissymmetry factor from the helicene skeleton.…”

Chirality‐Dependent Second‐Order Nonlinear Optical Effect in 1D Organic–Inorganic Hybrid Perovskite Bulk Single Crystal

“…It is worth noting that, the above mentioned chiral OIHPs are used in the detection of CPL only in the ultraviolet or visible light region and strongly dependent on the semiconductor properties of the materials. At present, chiral organic semiconducting molecules [42] and chiral plasmonic metamaterials [43] have been used for CPL detection in near‐infrared region (NIR), but the former highly depend on the semiconductor properties of the materials, while the later must be highly designed. According to our investigation, the detection of NIR CPL by chiral OIHPs is still blank due to the intrinsic absorption properties of the materials.…”