Supramolecular Nanostructures of Chiral Perylene Diimides with Amplified Chirality for High‐Performance Chiroptical Sensing

Abstract

Chiral supramolecular nanostructures with optoelectronic functions are expected to play a central role in many scientific and technological fields but their practical use remains in its infancy. Here, this paper reports photoconductive chiral organic semiconductors (OSCs) based on perylene diimides with the highest electron mobility among the chiral OSCs and investigates the structure and optoelectronic properties of their homochiral and heterochiral supramolecular assemblies from bottom-up self-assembly. Owing to the well-ordered supramolecular packing, the homochiral nanomaterials exhibit superior charge transport with significantly higher photoresponsivity and dissymmetry factor compared with those of their thin film and monomeric equivalents, which enables highly selective detection of circularly polarized light, for the first time, in visible spectral range. Interestingly, the heterochiral nanostructures assembled from co-self-assembly of racemic mixtures show extraordinary chiral self-discrimination phenomenon, where opposite enantiomeric molecules are packed alternately into heterochiral architectures, leading to completely different optoelectrical performances. In addition, the crystal structures of homochiral and heterochiral nanostructures have first been studied by ab initio X-ray powder diffraction analysis. These findings give insights into the structure-chiroptical property relationships of chiral supramolecular self-assemblies and demonstrate the feasibility of supramolecular chirality for high-performance chiroptical sensing.

Covalently Linked Perylene Diimide–Polydiacetylene Nanofibers Display Enhanced Stability and Photocurrent with Reversible FRET Phenomenon

“…Owing to their intriguing structural, optical, and electrical properties, perylene diimde (PDI) derivatives have been extensively investigated for use in a variety of systems including functional supramolecules, organic solar cells, organic field‐effect transistors (OFETs), and sensors . Because they undergo facile self‐assembly as a consequence of favorable π–π stacking, hydrogen bonding, and van der Waals interactions, certain PDI derivatives form well‐defined 1D nanostructures such as nanofibers and nanotubes . However, although these 1D PDI nanostructures serve as key components in optoelectronic devices, they often suffer from poor stability.…”

Outstanding Chiroptical Features of Thin Films of Chiral Oligothiophenes

“…Chirality in organic optoelectronic devices is a topic that is rapidly gaining interest . There is at least a two‐fold interest: in the first place it can constitute a means to drive and control the supramolecular order of π‐conjugated molecules constituting the active layers of the devices, and secondly it opens the way to highly specialized applications, such as producing (CP‐OLED), or detecting (CP‐OFET) circularly polarized (CP) light or specifically responding to analyte enantiomers in analytical sensors . Moreover, molecular chirality is a unique way to manipulate electron spins and to construct spin filters .…”

Homochiral Asymmetric‐Shaped Electron‐Transporting Materials for Efficient Non‐Fullerene Perovskite Solar Cells

“…This homochirality of two PhE groups at each end of the NDI core decreases the molecular symmetry of NDI‐PhE. Although introducing chiral groups onto π‐conjugated semiconducting cores has been reported previously, most studies have been focused on the chiroptical activity and formation of supramolecular nanostructures, rather than on the effect on solubility or solution processability with good film‐forming ability for electronic devices . The homochiral NDI‐PhE is synthesized by a condensation reaction between the chiral reagent ( R )‐1‐phenylethanamine and the achiral 1,4,5,8‐naphthalenetetracarboxylic dianhydride .…”

“…Although introducing chiral groups onto p-conjugated semiconducting cores has been reportedp reviously,m ost studies have been focused on the chiroptical activity and formationo fs upramolecular nanostructures, rather than on the effect on solubility or solution processability with good film-forminga bility for electronic devices. [43][44][45][46][47] The homochiral NDI-PhE is synthesized by ac ondensation reaction between the chiral reagent (R)-1-phenylethanamine andt he achiral 1,4,5,8-naphthalenetetracarboxylic dianhydride. [46,47] It can be expected that reduced molecular symmetry and increased free volumei ntroducedb yh omochiral asymmetric-shaped PhE groups enhance solubility and film-forming ability for electronic devices such as PSCs.…”