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Nanospace defined by unsaturated metal coordination sites opens up the possibility of controlling and templating chemical reactivity. Here, the authors show that a Fe(III) dicarboxylate framework with triangularly arranged metal sites can direct the [2+2+2] cyclisation of nitriles, alkynes and alkenes.

Zhanget al. show that simple geometry analysis can be used to predict how linker length and length ratios affect pore shape and size of porous coordination polymers. The accuracy of the predictions is confirmed by the synthesis of a series of 13 highly porous isoreticular frameworks.

Chemical adsorption of CO on open metal sites enables separation from other gases but leads to selectivity and stability issues. Quasi-open metal sites in metal–organic frameworks are proposed here, which are accessible only by CO-induced structural transformation, enabling CO separation to 9N purity.

Controlling and selectively altering the structure of materials opens up the possibility of modulating their physical properties. Here, the authors report a method for altering the properties of a coordination polymer, where the metal centres active molecular oxygen to oxidize the organic ligand.

The separation of high purity ethene from the mixed gaseous products of cracking poses significant obstacles. Here, the authors present a metal-organic framework which, in contrast to most absorbents, selectively binds the less polar ethane thus allowing the efficient collection of the target product.

While host–guest interplay has been well studied, there has been less work on utilizing the bulk property of guest. Here, the authors show that the jack-like motion of guest supramolecular aggregations can drastically modulate the thermal expansion properties of a three-dimensional hinge-like framework.

Host–guest materials open up the possibility of tuning physical properties based on the addition of appropriate guests. Here, a flexible, porous coordination polymer is reported, in which the addition of guest molecules significantly alters the thermal expansion properties as well as deforming the crystal lattice.

Molecular sieving separates larger from smaller molecules, but all molecules smaller than the pore adsorb, hindering selectivity. Here, a MOF is reported with both molecular sieving and gate-opening, separating intermediate-sized molecules from larger and smaller analogues.