Abstract 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 rotaxane selective for nitrate over more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions chloride, exhibits enhanced recognition anions relative to analogue. This elaborate interlocked receptor functions via novel dynamic pincer mechanism where...

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 robust dye molecules their rich photo- electrochemistry potential chirality make them ideal organic building blocks for optoelectronic materials. By exploiting new bay connectivity twisted PDIs, dynamic bis-PDI macrocycle (the "Pink Box") is realized which homochiral PDI–PDI π–π...

Macrocycles containing chiral organic dyes are highly valuable for the development of supramolecular circularly polarized luminescent (CPL) materials, where a preorganized framework is conducive to directing π–π self-assembly and delivering strong persistent CPL signal. Here, perylene diimides (PDIs) an excellent choice dye component because, alongside their tunable photophysical properties, functionalization PDI's core yields twisted, π-system, capable CPL. However, configurationally stable...

A novel dynamic [3]catenane consisting of a large four-station central macrocycle which incorporates bay tetrachloro-functionalized perylene diimide (PDI) unit and two triazolium anion-binding motifs, mechanically bonded with smaller isophthalamide-containing macrocycles, is constructed using an anion template synthetic methodology. Proton NMR, electronic absorption, fluorescence emission spectroscopies together molecular dynamics simulations are used to investigate the recognition-...

The powerful electron accepting ability of fullerenes makes them ubiquitous components in biomimetic donor–acceptor systems that model the intermolecular transfer processes Nature's photosynthetic center. Exploiting perylene diimides (PDIs) as cyclic host for noncovalent recognition is unprecedented, part because archetypal PDIs are also deficient, making dyad assembly formation electronically unfavorable. To address this, we report strategic design and synthesis a novel large, macrocyclic...

By addressing the challenge of controlling molecular motion, mechanically interlocked machines are primed for a variety applications in field nanotechnology. Specifically, designed manipulation communication pathways between electron donor and acceptor moieties that strategically integrated into dynamic photoactive rotaxanes catenanes may lead to efficient artificial photosynthetic devices. In this pursuit, novel [3]rotaxane shuttle consisting four-station bis-naphthalene diimide (NDI)...

Two bistable halogen and hydrogen bonding-naphthalene diimide [2]rotaxanes have been prepared the system incorporating a bond donor anion recognition site is demonstrated to exhibit superior induced translational motion of macrocyclic wheel component relative bonding analogue.

Helical assemblies of organic dyes are ubiquitous chiral materials, with valuable properties including chiroptical switching due to the dynamic nature supramolecular chirality. Herein, we report a novel bis‐perylene diimide macrocycle, which acts as discrete molecular model for assembly. Point chirality is installed through amino acid‐derived imide groups which, upon macrocyclization, translated into helical in perylene dimer. In solution, macrocycle’s switchable, both sign (+/‐) and...

Helical assemblies of organic dyes are ubiquitous chiral materials, with valuable properties including chiroptical switching due to the dynamic nature supramolecular chirality. Herein, we report a novel bis‐perylene diimide macrocycle, which acts as discrete molecular model for assembly. Point chirality is installed through amino acid‐derived imide groups which, upon macrocyclization, translated into helical in perylene dimer. In solution, macrocycle’s switchable, both sign (+/‐) and...

We report the preparation of [2]rotaxanes containing an electrochemically and optically active osmium(II) bipyridyl macrocyclic component mechanically bonded with cationic pyridinium axles. Such interlocked host systems are demonstrated to recognise sense anionic guest species as shown by (1)H NMR, luminescence electrochemical studies. The rotaxanes can be surface assembled on gold electrodes through anion templation under click copper(I)-catalysed Huisgen cycloaddition conditions form...

Abstract 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 rotaxane selective for nitrate over more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions chloride, exhibits enhanced recognition anions relative to analogue. This elaborate interlocked receptor functions via novel dynamic pincer mechanism where...

This work presents a synergy between organic electronics and supramolecular chemistry, in which host-guest complex is designed to function as an efficacious electronic material. Specifically, the noncovalent recognition of fullerene, phenyl-C61 -butyric acid methyl ester (PC61 BM), by alternating perylene diimide (P)-bithiophene (B) conjugated macrocycle (PBPB) results greater than five-fold enhancement electron mobility, relative alone. Characterization quantification binding fullerenes...

The Curtin–Hammett principle is used to understand the diastereoselective synthesis of a heterochiral over homochiral macrocycle, both which are configurationally stable chiral macrocycles.

Perylene diimide (PDI) dimers and higher aggregates are key components in organic molecular photonics photovoltaic devices, supporting singlet fission symmetry breaking charge separation. Detailed understanding of their excited states is thus important. This has proven challenging because interchromophoric coupling a strong function dimer architecture. Recently, macrocyclic PDI was reported which excitonic could be turned on off simply by changing the solvent. presents useful case where...

Perylene diimide (PDI) dimers and higher aggregates are key components in organic molecular photonics photovoltaic devices, supporting singlet fission symmetry breaking charge separation. Detailed understanding of their excited states is thus important. This has proven challenging because interchromophoric coupling a strong function dimer architecture. Recently, macrocyclic PDI was reported which excitonic could be turned on off simply by changing the solvent. presents useful case where...

Abstract Perylene diimide (PDI) dimers and higher aggregates are key components in organic molecular photonics photovoltaic devices, supporting singlet fission symmetry breaking charge separation. Detailed understanding of their excited states is thus important. This has proven challenging because interchromophoric coupling a strong function dimer architecture. Recently, macrocyclic PDI was reported which excitonic could be turned on off simply by changing the solvent. presents useful case...

Sustainable catalysts based on main-group elements have emerged as alternatives to expensive and environmentally unfriendly precious metal systems. Frustrated Lewis pairs (FLPs) are precluded from forming a classical adduct, displayed remarkably versatile reactivity in the fields of small-molecule activation catalysis. The initial reaction acid, base small molecule (e.g. H2) is formally termolecular, but viability this rationalised by pre-association acid an encounter complex. However, there...

Supramolecular chemistry encompasses critical aspects found throughout the chemical sciences. Despite its ubiquity, concept of supramolecular as a defined field research is relatively young, although roots run deep. Moving from strength to strength, Royal Society Chemistry's MASC meeting has grown local, UK-based conference truly international event. The 2023 edition was held at University Birmingham, where nearly 250 participants across four continents were brought together by their mutual...

Abstract Review: 603 refs.

N@C 60 is a paramagnetic endohedral fullerene species comprised of single nitrogen atom incarcerated within C carbon cage. Shielding the from external environment results in extremely long relaxation times its electron spin (T 1 = 0.375 ms, T 2 0.25 ms). This provides molecule with very sharp EPR signal, which undergoes observable dipolar broadening presence other species, suggesting that derivatives would be ideal candidates as probes for biological applications. 2–4 In order this to...