LAUSR

Abstract A photoswitchable [2]rotaxane with unique photogated macrocyclic shuttling is constructed by incorporating the photoswitchable azobenzene (AB) and nonphotoactive biphenyl (BP) units into the axle as two terminal recognition sites, bridged by a naphthalene (NAP) unit. The UV (λ = 379 nm)/blue (λ = 440–450 nm) lights triggered Z/E photoisomerization of the AB unit can drive the cyclobis(paraquat-p-phenylene) (CBPQT4+) macrocycle to shuttle between the two terminal recognition sites. Such macrocyclic translational movement can be photogated by a steric barrier generating from the green-light (λ = 520–525 nm)-triggered cycloaddition reaction between the NAP unit on the thread and a triazolinedione (TAD) additive. Upon standing in dark, the photocycloadduct undergoes disassociation which restores the phototriggered macrocyclic shuttling ability. The construction of such photogated photoresponsive molecular shuttle can provide new approach to improve the switching controllability of rotaxane, which is beneficial to fabricate rotaxane-based nanosystems and materials with high performance.