This review covers advances in anion complexation in the years 2011 and 2012. The review covers both organic and inorganic systems and also highlights the applications to which anion receptors can be ...applied such as self-assembly and molecular architecture, sensing, catalysis and anion transport.
This review covers advances in anion complexation in the years 2011 and 2012.
Porous materials are widely used in industry for applications that include chemical separations and gas scrubbing. These materials are typically porous solids, although the liquid state can be easier ...to manipulate in industrial settings. The idea of combining the size and shape selectivity of porous domains with the fluidity of liquids is a promising one and porous liquids composed of functionalized organic cages have recently attracted attention. Here we describe an ionic-liquid, porous, tetrahedral coordination cage. Complementing the gas binding observed in other porous liquids, this material also encapsulates non-gaseous guests-shape and size selectivity was observed for a series of isomeric alcohols. Three gaseous chlorofluorocarbon guests, trichlorofluoromethane, dichlorodifluoromethane and chlorotrifluoromethane, were also shown to be taken up by the liquid coordination cage with an affinity that increased with their size. We hope that these findings will lead to the synthesis of other porous liquids whose guest-uptake properties may be tailored to fulfil specific functions.
Supramolecular chemistry is a comparatively young field that to date has mainly been focused on building a foundation of fundamental understanding. With much progress in this area, researchers are ...seeking to apply this knowledge to the development of commercially viable products. In this review we seek to outline historical and recent developments within the field of supramolecular chemistry that have made the transition from laboratory to market, and to bring to light those technologies that we believe have commercial potential. In doing so we hope we may illuminate pathways to market for research currently being conducted.
Supramolecular chemistry has successfully built a foundation of fundamental understanding. However, with this now achieved, we show how this area of chemistry is moving out of the laboratory towards successful commercialisation.
In recent years, luminescent supramolecular coordination complexes (SCCs), including 2D‐metallacycles and 3D‐metallacages have been utilised for biomolecular analysis. Unlike small‐molecular probes, ...the dimensions, size, shape, and flexibility of these complexes can easily be tuned by combining ligands designed with particular geometries, symmetries and denticity with metal ions with strong geometrical binding preferences. The well‐defined cavities that result, in combination with the other non‐covalent interactions that can be programmed into the ligand design, facilitate great selectivity towards guest binding. In this Review we will discuss the application of luminescent metallacycles and cages in the binding and detection of a wide range of biomolecules, such as carbohydrates, proteins, amino acids, and biogenic amines. We aim to explore the effect of the structural diversity of SCCs on the extent of biomolecular sensing, expressed in terms of sensitivity, selectivity and detection range.
Cages as sensors: This Review describes the application of supramolecular coordination complexes (SCCs), including metal‐organic cages and metallacycles, as optical sensors for biologically significant analytes. It presents strategies to engineer an optical response to guest binding in SCCs and subsequent application in detecting biogenic amines, carboxylic acids, nucleotides and DNA, amino acids and proteins, carbohydrates and volatile organic molecules.
Metal–organic anion channels based on Zn10L15 pentagonal prisms have been prepared by subcomponent self‐assembly. The insertion of these prisms into lipid membranes was investigated by ion‐current ...and fluorescence measurements. The channels were found to mediate the transport of Cl− anions through planar lipid bilayers and into vesicles. Tosylate anions were observed to bind and plug the central channels of the prisms in the solid state and in solution. In membranes, dodecyl sulfate blocked chloride transport through the central channel. Our Zn10L15 prism thus inserts into lipid bilayers to turn on anion transport, which can then be turned off through addition of the blocker dodecyl sulfate.
Tune in to this new channel: Zn10L15 pentagonal prisms prepared by subcomponent self‐assembly were able to function as anion channels in phospholipid bilayers. The channels were blocked by amphiphilic dodecyl sulfate anions, which were bound by and plugged the central cavities of the channels (see picture).
Metallocycles and metallocages Xu, Lin; Haynes, Cally J. E; Lewis, James E. M
Dalton transactions : an international journal of inorganic chemistry,
06/2023, Letnik:
52, Številka:
24
Journal Article
Recenzirano
Guest Editors Lin Xu, Cally Haynes and James Lewis introduce the spotlight collection: Metallocycles and metallocages.
Coordination cages encapsulate a wide variety of guests in the solution state. This ability renders them useful for applications such as catalysis and the sequestration of precious materials. A ...simple and general method for the immobilization of coordination cages on alumina is reported. Cage loadings are quantified via adsorption isotherms and guest displacement assays demonstrate that the adsorbed cages retain the ability to encapsulate and separate guest and non‐guest molecules. Finally, a system of two cages, adsorbed on to different regions of alumina, stabilizes and separates a pair of Diels–Alder reagents. The addition of a single competitive guest results in the controlled release of the reagents, thus triggering their reaction. This method of coordination cage immobilization on solid phases is envisaged to be applicable to the extensive library of reported cages, enabling new applications based upon selective solid‐phase molecular encapsulation.
The adsorption of two metal–organic coordination capsules on alumina is quantified and the cages are shown to retain their ability to bind and release a molecular cargo following immobilization. The adsorbed cages are then used to stabilize the reagents of a Diels–Alder reaction prior to their subsequent release and reaction.
Supramolecular catalysis can emulate many features of enzymatic transformations. Now, a complex proton wire mechanism — enabling the dual activation of a nucleophile and an electrophile through ...reciprocal proton transfer — has been shown to operate during the β-glycosylation of sugars within a self-assembled capsule.
Diversity, equality, and inclusion (DEI/EDI) are pressing issues in chemistry and the natural sciences. In this Essay we share how an area‐specific approach is “calling in” the community so that it ...can act to address EDI issues, and support those who are marginalised. Women In Supramolecular Chemistry (WISC) is an international network that aims to support equality, diversity, and inclusion within supramolecular chemistry. WISC has taken a field‐specific approach using qualitative research methods with scientists to identify the support that is needed and the problems the supramolecular community needs to address. Herein, we present survey data from the community which highlight the barriers that are faced by those who take career breaks for any reason, a common example is maternity leave, and the importance of mentoring to aid progression post‐PhD. In conclusion, we set out an interdisciplinary and creative approach to addressing EDI issues within supramolecular chemistry.
Marginalisation can be experienced for many intersectional reasons including race, ethnicity, sexuality, religion, and gender. This Essay sets out a field‐specific approach to supporting equality, diversity, and inclusion in supramolecular chemistry as pioneered by an international network of Women In Supramolecular Chemistry (WISC). WISC aims to “call in” the community and to use qualitative approaches to set out a framework for addressing EDI.
PDF
