Macrocycle‐Based Charge Transfer Cocrystals with Dynamically Reversible Chiral Self‐Sorting Display Chain Length‐Selective Vapochromism to Alkyl Ketones

Abstract

Chirality‐driven self‐sorting plays an essential role in controlling the biofunction of biosystems, such as the chiral double‐helix structure of DNA from self‐recognition by hydrogen bonding. However, achieving precise control over the chiral self‐sorted structures and their functional properties for the bioinspired supramolecular systems still remains a challenge, not to mention realizing dynamically reversible regulation. Herein, we report an unprecedented saucer[4]arene‐based charge transfer (CT) cocrystal system with dynamically reversible chiral self‐sorting synergistically induced by chiral triangular macrocycle and organic vapors. It displays efficient chain length‐selective vapochromism toward alkyl ketones due to precise modulation of optical properties by vapor‐induced diverse structural transformations. Experimental and theoretical studies reveal that the unique vapochromic behavior is mainly attributed to the formation of homo‐ or heterochiral self‐sorted assemblies with different alkyl ketone guests, which differ dramatically in solid‐state superstructures and CT interactions, thus influencing their optical properties. This work highlights the essential role of chiral self‐sorting in controlling the functional properties of synthetic supramolecular systems, and the rarely seen controllable chiral self‐sorting at the solid‐vapor interface deepens the understanding of efficient vapochromic sensors.