Selective Synthesis of [2]Rotaxane Orientational Isomers With Precisely Arranged Luminogens: Toward Orientation‐Dependent Emissions for Information Storage and Encryption

Aiming at the precise synthesis of rotaxane orientational isomers and the further elucidation of attractive orientation effects, a novel steric hindrance‐controlled selective stopper exchange approach has been successfully developed. This method enables the facile and selective synthesis of six pairs of [2]rotaxane orientational isomers with precisely arranged luminogens, greatly enriching both the structural and functional diversity of such isomers. Notably, the resulting orientational isomers exhibit orientation‐dependent emission behaviors, particularly in wavelengths, photoluminescence quantum yields, and circularly polarized luminescence (CPL) performances, endowing them with great potential for information storage and encryption. This proof‐of‐concept study provides not only a practical and efficient strategy for the efficient synthesis of rotaxane orientational isomers, but also a novel platform for constructing chiral luminescent materials with desired properties for wide applications.