A Tutorial Review of the subtle supramolecular interactions influencing the outcomes of equilibrating systems, focusing on the dynamic covalent chemistry (DCC) of disulfide exchange reactions, is presented. We discuss the topics of cation-π interactions (2.1), hydrophobic effects (2.2), hydrogen bonding interactions (2.3) aromatic donor-acceptor interactions (2.4), and metal-ligand interactions (2.5) in the context of dynamic disulfide chemistry.

Porous materials are widely used in industry for applications that include chemical separations and gas scrubbing. These materials are typically porous solids, though 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 guestsshape-and size-selectivity was observed for a series of alcohol isomers. Three gaseous guests, chlorofluorocarbons CFC-11, CFC-12, and CFC-13, were also shown to be taken up by the liquid coordination cage with an affinity increasing 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. Recent work has shown that persistent cavities can be engineered into liquids, lending them permanent porosity. These new materials were initially proposed by James in 2007 1 , who recognised three distinct types of them. The simplest of these, Type I permanently porous liquids, consist of rigid hosts with empty cavities that are liquid in their neat state 2,3 , without requiring an additional solvent for fluidity 4-7. Metalorganic frameworks (MOFs) have also been observed to form liquid phases that are inferred to be porous 8,9 , although the high temperatures required preclude guest binding. Previously reported examples of porous liquids have included surface-modified hollow silica spheres 2 and hollow carbon spheres 3 , crown ether-functionalised organic cages 5 , and dispersions 4, 6 or slurries 7 of porous framework materials in ionic liquids. To date, applications of these materials have focussed on gas storage and separation 2,10,11. However, we are not aware of the binding of guest molecules larger than carbon dioxide or methane inside the cavities of porous liquids, restricting the potential application of these

Self-assembling macrobicyclic cryptand-type organic cages display remarkable self-sorting behavior with efficient component selection.

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Seven of the best: A dynamic combinatorial library of polycatenated tetrahedra was prepared by complexation between a dynamic Fe4L6 tetrahedral cage, constructed from ligands containing an electron‐deficient naphthalenediimide core, and an electron‐rich aromatic crown ether, 1,5‐dinaphtho[38]crown‐10. The highest order species in the library is the tetrahedral [7]catenane.Permissions: WILEY-VCH

We describe here the discovery of a new class of organic cages assembled from simple tri-and dithiol building blocks using dynamic combinatorial chemistry (DCC). These water-soluble disulfide-linked architectures containing up to eleven components are only generated upon templation by positively charged polyamine guests of appropriate shape and length such as spermine and spermidine. The overall response of the system as expressed in the pattern of peaks in an HPLC trace provides an unusual tool for the identification of the templating analyte.

The combination of a bent diamino(nickel(II) porphyrin) with 2-formylpyridine and Fe(II) yielded an Fe(II) 4 L6 cage. Upon treatment with the fullerenes C60 or C70 , this cage was found to transform into a new host-guest complex incorporating three Fe(II) centers and four porphyrin ligands, in an arrangement that is hypothesized to maximize π interactions between the porphyrin units of the host and the fullerene guest bound within its central cavity. The new complex shows coordinative unsaturation at one of the Fe(II) centers as the result of the incommensurate metal-to-ligand ratio, which enabled the preparation of a heterometallic cone-shaped Cu(I) Fe(II) 2 L4 adduct of C60 or C70 .

Self-assembly of multiple building blocks via hydrogen bonds into well-defined nanoconstructs with selective binding function remains one of the foremost challenges in supramolecular chemistry. Here, we report the discovery of a enantiopure nanocapsule that is formed through the self-assembly of eight amino acid functionalised molecules in nonpolar solvents through 48 hydrogen bonds. The nanocapsule is remarkably robust, being stable at low and high temperatures, and in the presence of base, presumably due to the co-operative geometry of the hydrogen bonding motif. Thanks to small pore sizes, large internal cavity and sufficient dynamicity, the nanocapsule is able to recognize and encapsulate large aromatic guests such as fullerenes C60 and C70. The structural and electronic complementary between the host and C70 leads to its preferential and selective binding from a mixture of C60 and C70.