Spontaneous Symmetry Breaking of Achiral Molecules Leading to the Formation of Homochiral Superstructures that Exhibit Mechanoluminescence

• Published in: Angewandte Chemie International Edition 2024-02, Vol.63 (8), p.e202318856-n/a
• Main Authors: Liu, Zheng‐Fei, Ye, Xin‐Yi, Chen, Lihua, Niu, Li‐Ya, Jin, Wei Jun, Zhang, Shaodong, Yang, Qing‐Zheng
• Format: Article
• Language: English
• Subjects: Broken symmetry; Chiral Crystal; Chirality; Conformation; Crystallization; Crystals; Functional materials; Mechanoluminescence; Optoelectronics; Polar Optical Functional Materials; Self-assembly; Spontaneous Chiral Resolution; Superstructures; Symmetry; Symmetry Breaking
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202318856

Chirality, with its intrinsic symmetry‐breaking feature, is frequently utilized in the creation of acentric crystalline functional materials that exhibit intriguing optoelectronic properties. On the other hand, the development of chiral crystals from achiral molecules offers a solution that bypasses the need for enantiopure motifs, presenting a promising alternative and thereby expanding the possibilities of the self‐assembly toolkit. Nevertheless, the rational design of achiral molecules that prefer spontaneous symmetry breaking during crystallization has so far been obscure. In this study, we present a series of six achiral molecules, demonstrating that when these conformationally flexible molecules adopt a cis‐conformation and engage in multiple non‐covalent interactions along a helical path, they collectively self‐assemble into chiral superstructures consisting of single‐handed supramolecular columns. When these homochiral supramolecular columns align in parallel, they form polar crystals that exhibit intense luminescence upon grinding or scraping. We therefore demonstrate our molecular design strategy could significantly increase the likelihood of symmetry breaking in achiral molecular synthons during self‐assembly, offering a facile access to novel chiral crystalline materials with unique optoelectronic properties. We designed a library of six achiral pyrene‐containing molecules and two counterexamples to demonstrate the powerful strategy for spontaneous symmetry breaking. When the polarity of the crystals resulting from symmetry breaking is coupled with the intrinsic photophysical property of pyrene moieties, the three polar crystals exhibit intense mechanoluminescence.