Abstract
A strategy for positioning, and loosely connecting, molecules in close proximity using mechanically interlocked handcuffs is described. The strategy is demonstrated using rylene diimides, creating dimeric structures in which two components are linked through pillar[5]arene/imidazolium rotaxanes. Investigation of the resulting molecules demonstrates intriguing and new properties that arise from placing these redox active dye molecules together, allowing interactions, whilst allowing the molecules to separate as required. In particular we observe excimer emission from a perylene diimide dimer handcuff and the formation of an unusual radical anion π-dimer upon double reduction of the same molecule. The latter exhibits a unique visible absorption profile for a PDI-based molecule. We demonstrate the flexibility of our approach by making an unprecedented mixed perylene diimide/naphthalene diimide dimer which also reveals interactions between the two components. Our synthetic strategy facilitates the creation of unusual dimeric structures and allows the investigation of intermolecular interactions and the effects they have on electronic and magnetic properties.
Highlights
The ability to organise molecules into prede ned con gurations lies at the heart of supramolecular chemistry
Reaction of perylene tetracarboxylic dianhydride with an imidazole group functionalized with an alkylamine arm leads to the formation of a bis-imidazole species (2) in which, and to the pillar[5]arene-functionalised species, the two arms are separated by the PDI aromatic core (Fig. 1). The simplicity of this approach allows, in principle, modi cation of the core of either of the handcuff components and we demonstrate this through the synthesis of a bis-imidazole functionalized naphthalene diimides (NDIs) (3)
Details of the calculations and assignment of the transitions observed for PDI and NDI models is discussed in Electronic supplementary information (ESI).† DFT modelling of 4 yielded results in which the calculated spectra are consistent with experiment for all charge states
Summary
The ability to organise molecules into prede ned con gurations lies at the heart of supramolecular chemistry. This shi to negative potential is consistent with the electrons populating an extended molecular orbital, as noted for the rst two reductions but the interaction between the PDI centres has changed.
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
