Self-assembled stereomutation with supramolecular chirality inversion

Abstract

Supramolecular chirality inversion is closely related to biological and chemical self-assembly systems. This review highlights the fundamental principles, various strategies, and promising applications of supramolecular chirality inversion.

Chiroptical regulation of macrocyclic arenes with flipping-induced inversion of planar chirality

“…Chiral inversion has been extensively studied in unimolecular systems and supramolecular polymers. 21 The application of chiral inversion has found applications in various fields such as molecular devices, 22 asymmetric catalysis, 23 enantiomeric separations 24 and chiral sensors. 25 While chiral inversion in chiral aggregates and polymers has been reported, studies on unimolecular chiral inversion systems are scarce.…”

Solvent-Directed Hierarchical Self-Assembly of Tetraphenylpyrazine-Cholesterol with Amplified Circularly Polarized Luminescence

“…The expression of hierarchical chirality plays a crucial role in determining the structures of chiral supramolecular materials and endows them with dynamic and smart functions. − The challenge is how to achieve the assembled nanostructures with chirality at different scales through the hierarchical self-assembly, due to the high complexity and tunable mutability affected by solvent, − assembly pathway, and other external stimuli − in solution assembly systems. In the recent years, we have developed a series of cholesterol-based building blocks to construct the metal-organic supramolecular polymers with dynamic supramolecular chirality regulation, including chirality amplification, helix-to-superhelix transformation and handedness inversion . The precise control of the subtle solute–solvent interactions provides a facile way to tune the chirality of the supramolecular polymer in the dynamic assembly process.…”

“…In the recent years, we have developed a series of cholesterol-based building blocks to construct the metal-organic supramolecular polymers with dynamic supramolecular chirality regulation, including chirality amplification, 22 helix-tosuperhelix transformation 23 and handedness inversion. 24 The precise control of the subtle solute−solvent interactions provides a facile way to tune the chirality of the supramolecular polymer in the dynamic assembly process. Thus, the efficient chirality transfer and hierarchical chirality can be successfully achieved by the solvent-directed self-assembly, which endowed the resultant supramolecular polymers with potential applications in asymmetric catalysis, 25−27 chiral recognition and separation, 28,29 and circularly polarized luminescence (CPL) materials.…”

Acceleration and deceleration of chirality inversion speeds in a dynamic helical metallocryptand by alkali metal ion binding

“…For example, chirality of discrete metal complexes and small organic molecules is reversed by ion recognition ( 15 – 22 ), molecular recognition ( 23 – 27 ), pH change ( 28 – 31 ), solvent exchange ( 32 – 35 ), etc. Inversion of supramolecular chirality has also been achieved by various kinds of external stimuli ( 36 – 38 ). Principally, this chirality inversion is driven by the reversal of the P / M preference in equilibrium before and after the external stimulation (Fig.…”