“Majority‐Rules” Effect on Supramolecular Chirality and Optoelectronic Properties of Chiral Tetrachloro‐Perylene Diimides

Abstract

Supramolecular chirality has attracted a great deal of attention as a platform for both fundamental study and chirality amplification in various research fields. Compared with the “sergeants‐and‐soldiers” principle, the “majority‐rules” principle, which affects chirality amplification in supramolecular systems, is rarely reported for nano/microstructures. Here, chiral tetrachloro‐substituted perylene diimides are synthesized that self‐assemble into chiral supramolecules with different degrees of enantiomeric excess (ee). Interestingly, it is found that quasi‐2D crystals are gradually transferred to 1D nanowires (NWs) with ee from 100% to 0%. In the racemic system, chiral self‐discrimination is observed due to the greater thermodynamic stability of heterochiral crystals than the homochiral counterparts, judging from the theoretical studies. Circular dichroism analysis indicates that the self‐assembled system with different ee values shows different peaks due to their unique molecular ordering for supramolecular exciton coupling. On measurement in optoelectronic devices, racemic 1D NWs show better charge transport ability than enantiomeric quasi‐2D crystals. These results provide guidelines for tuning the supramolecular chirality and optoelectronic performance of self‐assembled systems via the “majority‐rules” principle.

Investigation of the Amide Linkages on Cooperative Supramolecular Polymerization of Organoplatinum(II) Complexes

“…In supramolecular polymeric systems, chirality amplification is increasingly important for both fundamental science and practical applications [ 53 , 54 , 55 , 56 ]. It denotes the transfer of chiral information from molecular to supramolecular levels, in which “majority-rules” effects refer to the ability of a small enantiomeric imbalance to dictate the handedness of helical polymers [ 57 , 58 , 59 ]. With both ( S )- 2 and ( R )- 2 in hand, majority-rules experiments were performed by mixing the two enantiomers in different ratios at the total concentration of 4.00 × 10 −5 mol/L at 293 K. The full CD spectra showed the transition from pure ( R )- 2 ( ee = 100%) through the ( S )- 2 /( R )- 2 (1:1) ( ee = 0%) to pure ( S )- 2 ( ee = –100%) ( Figure 3 a).…”

Chiral supramolecular nanomaterials: From chirality transfer and amplification to regulation and applications

“…[ 16 ] Two distinct phenomena were identified that exert influence on the enhancement of chirality, commonly known as the “sergeants‐and‐soldiers” principle and the “majority‐rules” effects. [ 17 ] This phenomenon is commonly observed alongside a manifestation in the circular dichroism spectroscopy (CD) signals. [ 18–20 ] Figure 2 illustrates the underlying principles involved in the augmentation of chirality within self‐assembled systems.…”

Ligand‐Tuned Perylene Diimide‐Based Versatile Coordination Polymers for Photoluminescent Sensing and Optoelectronics

“…[29] To further investigate the potential uses of MetPDI-Cd CPs in optoelectronic applications, changes in their photocurrents upon the switching on and switching off of light were monitored (Figure 4). PDI-based materials have been introduced as photoactive materials in phototransistors; [54][55][56][57][58][59] although, there have been few reports of photoresponsivity using PDI-based CPs. To explore the photoconducting properties of PDI-based CPs, CP crystals were drop-casted onto chromium/gold electrodes patterned by photolithography on 300-nm SiO 2 /Si substrates; their I-V characteristics were investigated under ambient conditions (see details in the Supporting Information).…”