The synthesis of the first halogen bonding [3]rotaxane host system containing a bis‐iodo triazolium‐bis‐naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo‐triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion–rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the ¹H NMR anion binding results.

A novel dynamic [3]catenane consisting of a large four-station central macrocycle which incorporates a bay tetrachloro-functionalized perylene diimide (PDI) unit and two triazolium anion-binding motifs, mechanically bonded with two smaller isophthalamide-containing macrocycles, is constructed using an anion template synthetic methodology. Proton NMR, electronic absorption, and fluorescence emission spectroscopies together with molecular dynamics simulations are used to investigate the anion recognition- and solvent-dependent dynamic properties of the higher-order mechanically interlocked molecule. Importantly, unprecedented solvent-dependent and anion-binding-induced circumrotatory motion in a hetero[3]catenane system is demonstrated where the exotic dual rotary switching behavior provides a unique and sophisticated mechanism for optical anion sensing in competitive protic organic and aqueous–organic media.

This work showcases chiral complementarity in aromatic stacking interactions as an effective tool to optimize the chiroptical and electrochemical properties of perylene diimides (PDIs). PDIs are a notable class of robust dye molecules and their rich photo- and electrochemistry and potential chirality make them ideal organic building blocks for chiral optoelectronic materials. By exploiting the new bay connectivity of twisted PDIs, a dynamic bis-PDI macrocycle (the "Pink Box") is realized in which homochiral PDI-PDI π-π stacking interactions are switched on exclusively. Using a range of experimental and computational techniques, we uncover three important implications of the macrocycle's chiral complementarity for PDI optoelectronics. First, the homochiral intramolecular π-π interactions anchor the twisted PDI units, yielding enantiomers with half-lives extended over 400-fold, from minutes to days (in solution) or years (in the solid state). Second, homochiral H-type aggregation affords the macrocycle red-shifted circularly polarized luminescence and one of the highest dissymmetry factors of any small organic molecule in solution (g_lum = 10^-2 at 675 nm). Finally, excellent through-space PDI-PDI π-orbital overlap stabilizes PDI reduced states, akin to covalent functionalization with electron-withdrawing groups.

Macrocycles containing chiral organic dyes are highly valuable for the development of supramolecular circularly polarized luminescent (CPL) materials, where a preorganized chiral framework is conducive to directing π-π self-assembly and delivering a strong and persistent CPL signal. Here, perylene diimides (PDIs) are an excellent choice for the organic dye component because, alongside their tunable photophysical and self-assembly properties, functionalization of the PDI's core yields a twisted, chiral π-system, capable of CPL. However, configurationally stable PDI-based macrocycles are rare, and those that are also capable of π-π self-assembly beyond dimers are unprecedented, both of which are advantageous for robust self-assembled chiroptical materials. In this work, we report the first bay-connected bis-PDI macrocycle that is configurationally stable (ΔG^⧧ > 155 kJ mol^-1). We use this chirally locked macrocycle to uncover new knowledge of chiral PDI self-assembly and to perform new quantitative CPL imaging of the resulting single-crystal materials. As such, we discover that the chirality of a 1,7-disubstituted PDI provides a rational route to designing H-, J- and concomitant H- and J-type self-assembled materials, important arrangements for optimizing (chir)optical and charge/energy transport properties. Indeed, we reveal that CPL is amplified in the single crystals of our chiral macrocycle by quantifying the degree of emitted light circular polarization from such materials for the first time using CPL-Laser Scanning Confocal Microscopy.