Liquid crystal-mediated self-assembly of copper nanoclusters with induced circular dichroism and amplified circularly polarized luminescence

Abstract

Elucidating the mechanism of chiral transfer is key to regulating chiral expression and generalizing the structure–property relationship of chiral functional systems. However, it is still an important challenge to select novel building blocks to achieve chiral induction, chiral transfer and chiral modulation. Liquid crystals (LCs) can be considered as promising smart soft materials due to their responsiveness and adaptability. Confining chiral metal nanoclusters (NCs) in an achiral LC phase to construct chiral LCs provides an expanded strategy for the self-assembly of chiral metal NCs in different matrices. Herein, chiral glutathione-stabilized copper NCs (G-SH-Cu NCs)/polyoxyethylene tert-octylphenyl ether (TX-100) LCs were constructed and systematically investigated. The results showed that the introduction of G-SH-Cu NCs into TX-100 LCs induced the generation of supramolecular chirality. More interestingly, the circular dichroism (CD) handedness can be controlled by changing the amount of TX-100 or G-SH-Cu NCs; when the ratio of G-SH-Cu NCs and TX-100 was proportionally matched, the strength of the noncovalent interactions was sufficient to induce chiral inversion. Meanwhile, TX-100 LCs provide effective confinement of G-SH-Cu NCs, which improves the expression of asymmetry at the aggregation level and induces a 2-fold enhancement of the circularly polarized luminescence (CPL) signal. This work realizes the spatial amplification of chirality through dopants in LCs, which provides an effective method for accurately regulating the supramolecular chirality of metal NCs in the LC phase.