Themed collection In celebration of Paul Beer’s 60th Birthday
Exploiting the dithiocarbamate
ligand in metal-directed self-assembly
This Perspective examines the versatility of the dithiocarbamate ligand in metal-directed self-assembly. The ligand has been utilised to form a variety of well-defined architectures, which can participate in host–guest chemistry and in stabilising gold nanoparticles.
Halogen bonding anion recognition
The development of solution-based anion receptor molecules which exploit halogen bonding interactions is an emerging area of research. This Feature Article reviews recent advances which have been made in this rapidly developing field, surveying the use of iodoperfluoroarene, haloimidazolium and halotriazole/triazolium halogen-bond-donor motifs in anion receptor design and describing the application of mechanically interlocked rotaxane and catenane frameworks as halogen bonding anion host systems.
Mechanically interlocked and switchable molecules at surfaces
This feature article summarises the developments made in the surface assembly and characterisation of mechanically interlocked molecules, including recent progress in exploiting templating methods to interlock molecular systems on surfaces.
Anion-templated assembly of interpenetrated and interlocked structures
The rational development of a general anion templation strategy for the construction of interpenetrated and interlocked molecular structures based upon the coupling of anion recognition with ion-pairing is described.
Anion recognition and redox sensing amplification by self-assembled monolayers of 1,1′-bis(alkyl-N-amido)ferrocene
Surface pre-organisation within robust amidoferrocene self-assembled monolayers can be exploited in the selective electrochemical sensing of anions in both organic and aqueous media.
host rotaxane and catenane structures for sensing charged guest species via optical and electrochemical methodologies
Interlocked host molecules are demonstrated to exhibit high degrees of molecular recognition which, when coupled to appended reporter groups, make them highly promising candidates for the development of molecular sensors.
Metal ions in the synthesis of interlocked molecules and materials
We discuss the various roles that metal ions play, and their advantages, in the synthesis of mechanically interlocked materials.
Progress in the synthesis and exploitation of catenanes since the Millennium
Key developments including the utilization of new metal cation and anion templates, dynamic combinatorial chemistry, molecular machines and the incorporation of catenanes onto surfaces and into metal organic frameworks are reviewed.
Meldola Medal Lecture. Redox responsive macrocyclic receptor molecules containing transition metal redox centres
Sulfate anion templation of macrocycles, capsules, interpenetrated and interlocked structures
The potential of the sulfate dianion to template the formation of complex molecular architectures including helixes, capsules, and interlocked systems is discussed.
Anion templated assembly of mechanically interlocked structures
A new strategic anion templation methodology has been developed for the synthesis of interpenetrated pseudorotaxane, rotaxane and catenane structures, designed with a view to producing new highly selective anion receptors after template removal.
Selective perrhenate recognition in pure water by halogen bonding and hydrogen bonding alpha-cyclodextrin based receptors
Alpha-cyclodextrin based anion receptors containing halogen and hydrogen bond donor motifs display selective association of perrhenate in neutral aqueous media.
Neutral iodotriazole foldamers as tetradentate halogen bonding anion receptors
A tetradentate halogen bond donor foldamer receptor framework is shown to exhibit enhanced anion recognition and chiral discrimination properties.
Enhancing the enantioselective recognition and sensing of chiral anions by halogen bonding
Novel halogen bonding chiral (S)-1,1′-bi-2-naphthol-based receptor molecules significantly enhance enantioselective anion recognition and electrochemical sensing compared to their hydrogen bonding analogues.
Halogen bonding-enhanced electrochemical halide anion sensing by redox-active ferrocene receptors
The first redox-active halogen bonding anion receptors display larger electrochemical voltammetric responses to halide binding compared to their hydrogen bonding analogues.
Anion recognition in water by a rotaxane containing a secondary rim functionalised cyclodextrin stoppered axle
The synthesis of a water soluble rotaxane is reported using hydrophilic secondary rim functionalised permethylated β-cyclodextrin derivatives as the axle stopper groups. The rotaxane recognises halide anions in pure water with impressive selectivity over sulfate.
Superior perrhenate anion recognition in water by a halogen bonding acyclic receptor
The first example of perrhenate anion binding and fluorescence sensing in water by a halogen bond donor is reported.
Nitrate anion templated synthesis of a catenane for nitrate recognition in organic–aqueous solvent media
The first example of a catenane synthesised using a nitrate anion template is demonstrated. The resulting interlocked host is capable of selectively recognising nitrate over a range of more basic oxoanions in a competitive organic–aqueous solvent mixture.
Neutral rotaxane host systems that recognise halide anions in aqueous solvent mixtures
Four neutral rotaxane host systems, synthesised via anion templation, are shown to recognise halide anions in aqueous solvent mixtures.
Nitrate anion templated assembly of a rotaxane for selective nitrate recognition in aqueous solvent mixtures
The first nitrate templated synthesis of an interlocked structure is reported. The resulting rotaxane host selectively recognises nitrate in preference to other mono-oxoanions in aqueous solvent mixtures.
halogen bonding in crystals and anion-templated pseudorotaxanes
The 2-iodoimidazolium group is exploited in the anion-templated assembly of pseudorotaxanes with isophthalamide containing macrocycles.
gold nanoparticles for the detection of sulfur mustard by displacement assay
The dansyl fluorophore ligated to gold nanoparticles via imidazole and amine groups affords conjugates capable of detecting micromolar concentrations of the chemical warfare agent sulfur mustard by a fluorescence switching ‘ON’ displacement assay.
rotaxane capable of binding and electrochemically sensing chloride and sulfate anions
A redox-active rotaxane exhibits different binding and electrochemical responses to chloride and sulfate anions in competitive solvent media.
Anion induced and inhibited circumrotation of a catenane
The first example of a catenane capable of performing circumrotation via an anion switching methodology is described; of particular interest is a conformational locking mechanism which results from chloride coordination in the catenane binding cavity.
Cooperative AND receptor for ion-pairs
A new calixdiquinone species has been found to bind simple ion-pair systems strongly where no discernible affinity for either of the free ions is observed.
Anion directed synthesis of a hydrogensulfate selective luminescent rotaxane
A new photo-active rhenium(I) bipyridyl based rotaxane has been synthesised making use of a strategy founded on anion templation. By virtue of the unique interlocked structural cavity, the rotaxane selectively senses hydrogensulfate using luminescence spectroscopy.
Indolocarbazoles: a new family of anion sensors
Simple preorganised indolo[2,3-a]carbazole derivatives are shown to recognise and sense anionic guest species using fluorescence spectroscopy.
Halide anion directed assembly of luminescent pseudorotaxanes
A series of new photo-active rhenium(I) bipyridyl based pseudorotaxane complexes is assembled via halide anion templation.
Calixarene based dendrimers
The synthesis of
The binding of difunctional neutral guest molecules by novel bis(tripyrrolyl) cryptands
Dendrimers based on multiple 1,4,7-triazacyclononane derivatives
Superior anion induced shuttling behaviour exhibited by a halogen bonding two station rotaxane
Two bistable halogen and hydrogen bonding-naphthalene diimide rotaxanes have been prepared and the system incorporating a halogen bond donor anion recognition site is demonstrated to exhibit superior anion induced translational motion of the macrocyclic wheel component relative to the hydrogen bonding analogue.
Solution and surface-confined chloride anion templated redox-active ferrocene catenanes
The first ferrocene containing catenanes, in solution and on a surface, have been prepared by chloride anion templation.
Cation-induced molecular motion of spring-like
The synthesis and cation recognition studies of two novel heteroditopic catenanes that are capable of exhibiting cation induced reversible rotary motion is described. Barium cation complexation triggers a partial intra-ring rotation of the catenanes which is reversed upon addition of sulfate.
A dual-functional tetrakis-
imidazolium macrocycle for supramolecular assembly
A new versatile tetrakis-imidazolium macrocycle for use in supramolecular applications is reported. It displays excellent affinities for π-electron rich neutral guests such as 1,5-dihydroxynaphthalene derivatives and TTF, providing opportunities for the construction of interlocked molecules, as well as exhibiting extensive and potent anion coordination chemistry.
Cationic all-halogen bonding rotaxanes for halide anion recognition
Copper(II)-directed synthesis of neutral heteroditopic rotaxane ion-pair host systems incorporating hydrogen and halogen bonding anion binding cavities
Neutral heteroditopic rotaxane ion-pair host systems were synthesised via a copper(II)-directed metal template strategy and shown to undergo cooperative anion recognition with a co-bound zinc(II) cation.
Tripodal halogen bonding iodo-azolium receptors for anion recognition
The preparation and anion binding properties of 1,3,5-tri-substituted benzene platform-based tripodal receptors containing halogen bonding (XB) iodo-imidazolium and iodo-triazolium motifs, and hydrogen bonding (HB) analogues are described.
Halogen bonding rotaxanes for nitrate recognition in aqueous media
Incorporating halogen bonding into an interlocked rotaxane anion host system results in unprecedented nitrate recognition in 90% water.
Chelated charge assisted halogen bonding enhanced halide recognition by a pyridinium-iodotriazolium axle containing rotaxane
A dicationic halogen bonding rotaxane displays enhanced binding and selectivity for bromide over other halides and nitrate and dihydrogen phosphate oxoanions in contrast to an all hydrogen bonding counterpart which is attributed to chelated charge assisted halogen bonding interactions.
Substituent effects on fluoride binding by lanthanide complexes of DOTA-tetraamides
Fluoride binding by lanthanide complexes of a range of DOTA tetraamides changes the magnetic anisotropy at the metal centre from an easy axis to an easy plane.
Axial fluoride binding by lanthanide DTMA complexes alters the local crystal field, resulting in dramatic spectroscopic changes
Dramatic changes are observed in both the NMR and luminescence spectra of LnDTMA complexes on addition of fluoride, consistent with a change in the nature of the magnetic anisotropy at the paramagnetic lanthanide centre.
Contrasting anion recognition behaviour exhibited by halogen and hydrogen bonding rotaxane hosts
A rotaxane anion host that switches selectivity from dihydrogen phosphate to the halides upon substituting a hydrogen bond donor group for a halogen bond donor group within the axle component is described.
Halogen- and hydrogen-bonding triazole-functionalised porphyrin-based receptors for anion recognition
Halogen-bonding iodotriazole anion recognition groups have been integrated into a picket-fence zinc(II)-metalloporphyrin scaffold to produce a receptor with enhanced halide anion recognition and sensing applications.
A rotaxane host system containing integrated triazole C–H hydrogen bond donors for anion recognition
A novel bis-triazole pyridinium axle containing rotaxane, prepared by a chloride anion templated ring closing metathesis clipping strategy, exhibits selectivity for halide anions over oxoanions with a notable preference for bromide being shown amongst the halides.
Haloaurate and halopalladate imidazolium salts: structures, properties, and use as precursors for catalytic metal nanoparticles
We report the synthesis and structural characterisation of a series of gold- and palladium-containing imidazolium salts. The reduction of these salts can give nanoparticles stabilised either by surfactant or carbene species which demonstrate catalytic activity even while ligands are attached to the metal surface.
Investigating the effect of macrocycle size in anion templated imidazolium-based interpenetrated and interlocked assemblies
The effect of varying the size of the macrocycle component on the formation of anion templated imidazolium interpenetrated assemblies and on the recognition properties of analogous interlocked rotaxane host systems is investigated.
meta-xylenediamide macrocycle containing rotaxane anion host system constructed by a new synthetic clipping methodology
A meta-xylenediamide containing rotaxane is prepared by a novel synthetic procedure, and exhibits selective halide anion recognition.
Amplification of anion sensing by
disulfide functionalized ferrocene and ferrocene- calixarene receptors adsorbed onto gold surfaces
Anion sensing by ferrocene functionalized receptors is significantly enhanced when adsorbed at gold surfaces.
Tuning the strength and selectivity of ion-pair recognition using heteroditopic calixarene-based receptors
The fine tuning of selectivity and strength of cooperative ion-pair recognition using heteroditopic calixarene-based receptors has been achieved. These modulations in binding properties are found to depend critically on the cation binding site and the macrocyclic nature of the receptors.
Novel halo-derivatised calixtubes exhibit exceptional selectivity for potassium as evidenced by NMR, ESMS and molecular modelling studies.
A new carboxylate anion selective cobaltocenium calixarene receptor
Solvent dependent anion selectivity exhibited by neutral ferrocenoyl receptors
Anion selective recognition and optical/electrochemical sensing by novel transition-metal receptor systems
Synthesis and X-ray crystal structure of a new redox-active calixarene containing a totally included ethanol molecule
Dimer and trimer calixarenes containing multiple metallocene redox-active centres. Single-crystal X-ray structure of a bis(ferrocene)-bis(p-t-butylcalix-arene) hydrophobia host molecule
The synthesis and electrochemistry of novel redox responsive molybdenum complexes containing cyclic polyether cation binding sites
The synthesis of a novel Schiff base bis(crown ether) ligand containing recognition sites for alkali and transition metal guest cations
Synthesis of novel metallocene bis(crown ethers). Potassium selective intramolecular sandwich-type complexation observed by fast atom bombardment mass spectrometry
Pentaco-ordinate phosphorus compounds by nucleophilic addition to activated alkenes
About this collection
We are delighted to present this collection of 60 articles to celebrate the work of Paul Beer, on the occasion of his 60th birthday. This special collection has been organised by Chris Serpell and Phil Gale. During his research career, Paul has published more than 200 articles in Royal Society of Chemistry journals, participated in 15 themed issues, and notably published 83 times in ChemComm. This collection highlights his most recent work across a range of our journals, as well as a selection of his articles throughout his career. We would like to wish him a very happy birthday!