Supramolecular chirality: a caveat in assigning the handedness of chiral aggregates

Abstract

Exciton chirality rule for assigning the handedness of supramolecular aggregates is rephrased by accounting for the nature of intermolecular interactions.

Multi‐Modal Chiral Superstructures in Self‐Assembled Anthracene‐Terminal Amino Acids with Predictable and Adjustable Chiroptical Activities and Color Evolution

“…[17][18][19][20][21][22][23][24][25][26][27][28][29][30] Nevertheless,t he structure-property relationship between chiral assemblies and CPL responses still remain ambiguity. [16,31] Up to now,o nly absolute configuration (enantiomer-resolved) influence on the opposite handedness is confirmed. Although Nakanishi et al proposed an exciton coupling rule that positive-thennegative Cotton effect corresponds to the clockwise screw sense between two electric transition dipole moments,itdoes not has ag eneric validity.…”

“…Over the past five years, lot of efforts have been put in tuning CPL colors, boosting the dissymmetry g‐factor and expanding potential applications [17–30] . Nevertheless, the structure‐property relationship between chiral assemblies and CPL responses still remain ambiguity [16, 31] . Up to now, only absolute configuration (enantiomer‐resolved) influence on the opposite handedness is confirmed.…”

“…Although Nakanishi et al. proposed an exciton coupling rule that positive‐then‐negative Cotton effect corresponds to the clockwise screw sense between two electric transition dipole moments, it does not has a generic validity [31] . Addressing this issue would greatly guide the rational design and fabrication of CPL and other chiroptical materials towards diversified applications.…”

Light-directed trapping of metastable intermediates in a self-assembly process

“…3c) shows that the intensity of the vibronic peak at 580 nm associated with nanoribbons decreases while that of the peak at 550 nm arising from nanotubes increases. The shape and peak position of UV-visible absorption spectra compared to those of unassembled PDI monomers indicate that 1-R in the nanoribbons and nanotubes are stacked in the form of H-aggregates (twisted π-stacking) with left-handed and right-handed helical structures, respectively 54 . In addition, as J-type aggregates of PDI chromophores generally exhibit absorption at above 600 nm 45 , both nanoribbons and nanotubes are believed to be molecularly stacked in H-type forms.…”

Multi‐Modal Chiral Superstructures in Self‐Assembled Anthracene‐Terminal Amino Acids with Predictable and Adjustable Chiroptical Activities and Color Evolution

“…Although Nakanishi et al proposed an exciton coupling rule that positive-thennegative Cotton effect corresponds to the clockwise screw sense between two electric transition dipole moments,itdoes not has ag eneric validity. [31] Addressing this issue would greatly guide the rational design and fabrication of CPL and other chiroptical materials towards diversified applications.…”