biostudies-literaturePearce NRCUK | Engineering and Physical Sciences Research Council (EPSRC)RCUK | Engineering and Physical Sciences Research CouncilDiamond Light SourceEngineering and Physical Sciences Research Council415https://www.ebi.ac.uk/biostudies/studies/S-EPMC8776946biostudies-literatureUnknown13(1)The ability to control photoinduced charge transfer within molecules represents a major challenge requiring precise control of the relative positioning and orientation of donor and acceptor groups. Here we show that such photoinduced charge transfer processes within homo- and hetero-rotaxanes can be controlled through organisation of the components of the mechanically interlocked molecules, introducing alternative pathways for electron donation. Specifically, studies of two rotaxanes are described: a homo[3]rotaxane, built from a perylenediimide diimidazolium rod that threads two pillar[5]arene macrocycles, and a hetero[4]rotaxane in which an additional bis(1,5-naphtho)-38-crown-10 (BN38C10) macrocycle encircles the central perylenediimide. The two rotaxanes are characterised by a combinatNature communicationsSelective photoinduced charge separation in perylenediimide-pillar[5]arene rotaxanes.PMC8776946CY21755EP/S002995/1EP/S002995/2Reynolds KEAKayal SYamano ASun XZMalagreca FSchurmann CJPearce NIto SArgent SPGeorge MWDavies ESChampness NRfalseSelective photoinduced charge separation in perylenediimide-pillar[5]arene rotaxanes.The ability to control photoinduced charge transfer within molecules represents a major challenge requiring precise control of the relative positioning and orientation of donor and acceptor groups. Here we show that such photoinduced charge transfer processes within homo- and hetero-rotaxanes can be controlled through organisation of the components of the mechanically interlocked molecules, introducing alternative pathways for electron donation. Specifically, studies of two rotaxanes are described: a homo[3]rotaxane, built from a perylenediimide diimidazolium rod that threads two pillar[5]arene macrocycles, and a hetero[4]rotaxane in which an additional bis(1,5-naphtho)-38-crown-10 (BN38C10) macrocycle encircles the central perylenediimide. The two rotaxanes are characterised by a combinat2022-01-01T00:00:00Z2022 Jan2026-07-16T15:28:46.601Z2025-04-05T11:17:59.214ZS-EPMC87769463505844010.1038/s41467-022-28022-3