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Selective lithium halide ion-pair sensing by a dynamic metalloporphyrin [2]rotaxane.
Dalton Trans
January 2025
Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, OX1 3TA, UK.
Article Synopsis
- A new type of [2]rotaxane is developed that features a zinc(II) metalloporphyrin axle and a special macrocycle, which can effectively recognize and sense lithium halide ion pairs through optical methods.
- Research using H NMR and UV-visible absorption indicates that the interaction between the macrocycle and the zinc(II) axle leads to a significant change in the rotaxane's structure.
- Titration experiments reveal that when lithium halide pairs bind to the system, they disrupt the mechanical bond, allowing the macrocycle to move and enhance the recognition and sensing capabilities of lithium halide salts.
Mechanically interlocked host systems for ion-pair recognition.
Chem Commun (Camb)
October 2024
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford OX1 3TA, UK.
The ever-increasing interest directed towards the construction of host architectures capable of the strong and selective recognition of various ionic species of biological, medical and environmental importance has identified mechanically interlocked molecules (MIMs), such as rotaxanes and catenanes, as potent host systems, owing to their unique three-dimensional topologically preorganised cavity recognition environments. Ion-pair receptors are steadily gaining prominence over monotopic receptor analogues due to their enhanced binding strength and selectivity, demonstrated primarily through acyclic and macrocyclic heteroditopic host systems. Exploiting the mechanical bond for ion-pair recognition through the strategic design of neutral heteroditopic MIMs offers exciting opportunities to accomplish potent and effective binding while mitigating competing interactions from the bulk solvent and counter-ions.
View Article and Find Full Text PDFIon-Pairing Stereodynamic Probes for Circular Dichroism Chiral Sensing of Amines.
Inorg Chem
September 2024
Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova, Italy.
Tris(2-pyridylmethyl)amine () and tris(2-phenolmethyl)amine () metal complexes have been extensively used for catalysis and molecular recognition applications. In particular, due to their ability to form stereodynamic complexes through the helical arrangement of the ligand around the metal in a propeller shape, chiroptical sensing has been extensively investigated. In particular, the capability of the analyte, usually a Lewis base, to bind the metal complex has been the predominant recognition motif.
View Article and Find Full Text PDFDetermining Ion-Pair Binding Affinities of Heteroditopic Receptor Systems.
Chemistry
December 2024
Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, OX1 3TA, UK.
Determining ion-pair affinities in heteroditopic receptor systems presents a persistent and significant challenge. The plethora of technical and experimental problems implicated in measuring ion-pair affinities have encouraged the use of several expedient experimental practices as a means of characterising ion-pair recognition behaviour. Exploiting a model heteroditopic receptor system, we interrogate the reliability of these methods and demonstrate that these commonly used techniques can be highly questionable and without extreme care can lead to incorrect conclusions.
View Article and Find Full Text PDFSelective sodium halide over potassium halide binding and extraction by a heteroditopic halogen bonding [2]catenane.
Chem Sci
August 2024
Chemistry Research Laboratory, Department of Chemistry, University of Oxford Mansfield Road Oxford OX1 3TA UK
The synthesis and ion-pair binding properties of a heteroditopic [2]catenane receptor exhibiting highly potent and selective recognition of sodium halide salts are described. The receptor design consists of a bidentate halogen bonding donor motif for anion binding, as well as a di(ethylene glycol)-derived cation binding pocket which dramatically enhances metal cation affinity over previously reported homo[2]catenane analogues. H NMR cation, anion and ion-pair binding studies reveal significant positive cooperativity between the cation and anion binding events in which cation pre-complexation to the catenane subsequently 'switches-on' anion binding.
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