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

Abstract

Deep understanding of structure–property relationship between packing of chiral building units and their chiroptical behaviors would significantly facilitate the rational design and fabrication of the emerging chiroptical materials such as circularly polarized luminescence (CPL) emissive materials. In this paper, we unveil the universal existence of supramolecular tilt helical superstructures in self‐assembled π‐conjugated amino acid derivatives. A series of coded amino acid methyl esters were conjugated to anthracene segments at N‐terminus, which afforded 21 and 31 symmetry supramolecular tilt chirality in solid‐states. Helical assemblies enabled diversified Cotton effects and CPL performances, which were in accordance with the tilted chirality between anthracene segments. Such correlation shows fine universality, whereby the chiroptical prediction could be realized. Furthermore, on top of charge‐transfer complexation, manipulation of CPL emission colors and handedness were realized.

Ionic liquid crystals based on amino acids and gemini surfactants: tunable phase structure, circularly polarized luminescence and emission color

“…In particular, 16-Ph-16·2Trp ILC possessed a pair of exciton peaks at 355 nm (−) and 404 nm (+), which are attributed to the stronger π–π interaction between the indole moiety, benefitting from the introduction of the phenyl spacer. 60–62 The appearance of the exciton-couplet Cotton effect implies that the chiral self-assembly structure of the 16-Ph-16·2Trp ILC was different from that of the 16-2-16·2Trp ILC. As mentioned above, 16-Ph-16·2Trp could self-assemble into a Col h mesophase in the trimer mode, while 16-2-16·2Trp LC formed a SmC* phase.…”

“…It should be noted that the handedness of the CD and CPL are not necessarily consistent. 62,64,65 Although these complexes bore the same l -configurations, they could self-assemble into LC superstructures with inverse chirality, which further emitted disparate circularly polarized lights. Notably, the generation of the CPL signal was dependent on the well-organized LC structures.…”

Frontiers in circularly polarized luminescence: molecular design, self-assembly, nanomaterials, and applications

“…In 2018, Liu and co-workers [88] used the naphthalene-based backbone structure substituted with L-histidine moiety to form CPL-active organogel materials, and the CPL signals were efficiently enlarged via non-covalent interactions upon the addition of non-fluorescent achiral benzoic acids. Xing's group [89][90][91][92][93] prepared a series of novel CPL-active materials by evolving the molecular chirality to the supramolecular level or the macroscopic level through supramolecular self-assembly process. In 2021, they observed the universal existence of supramolecular tilt helical superstructures in self-assembled π-conjugated amino acid derivatives and unveiled the manipulation mechanism of CPL emission wavelengths and handedness based on charge-transfer complexation [93].…”

“…Xing's group [89][90][91][92][93] prepared a series of novel CPL-active materials by evolving the molecular chirality to the supramolecular level or the macroscopic level through supramolecular self-assembly process. In 2021, they observed the universal existence of supramolecular tilt helical superstructures in self-assembled π-conjugated amino acid derivatives and unveiled the manipulation mechanism of CPL emission wavelengths and handedness based on charge-transfer complexation [93]. Recently, Duan's group [94] investigated CPL-active materials of the supramolecular self-assembled system (g lum = −1.1 × 10 −2 , Φ F = 0.80) driven by areneperfluoroarene interactions between chiral polycyclic aromatic hydrocarbons and octafluoronaphthalene.…”

Surfactant-induced chirality transfer, amplification and inversion in a cucurbit[8]uril–viologen host–guest supramolecular system

“…Besides, as the chiral supramolecular structures are vulnerable to the external environment, it would be challenging to characterize and manipulate multiple chiral behaviors in a supramolecular structure, especially for complicated supramolecular coassemblies that include two or more components. 32–35…”