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Inverse vulcanization (IV) generates sulfur-rich functional polymers from elemental sulfur and organic crosslinkers, but the harsh reaction conditions required limit the scope of suitable crosslinkers. Now, a photoinduced IV has been shown to proceed at ambient temperatures, enabling the use of volatile and gaseous alkenes and alkynes as crosslinkers and broadening the range of products.

The construction of porous solids from discrete organic molecules usually involves the formation of regular porous crystals. In this study, a covalent scrambling reaction gives molecules with a range of shapes that do not pack effectively — manipulation of the reagent ratio allows fine control of porosity.

Interlocked molecules commonly include one (or more) monocyclic component — examples comprising bicyclic or tricyclic structures are much more rare and usually involve metal–ligand coordination or additional templates. Now, the dynamic self-assembly of twenty organic molecules in a one-pot synthesis has been shown to produce tetrahedral covalent cages, which interpenetrate during the process to form triply interlocked dimers.

A porous organic-cage molecule is shown to exhibit unprecedented performance for the separation of rare gases, with selectivity arising from a precise size match between the rare gas and the organic-cage cavity.

Porous materials are technologically important for a wide range of applications, such as catalysis and separation. Covalently bonded organic cages can now be assembled into crystalline microporous materials, and their porosity is found to be intrinsic to their molecular cage structure.

Inverse vulcanization allows stable polymers to be made from elemental sulfur, but development is restricted by cross-linkers and the elevated temperatures required. Here the authors report a catalytic method for a wide range of cross-linkers and found a reduced reaction temperature and reaction time is required.

The thermal and mechanical properties of inverse vulcanized polymers are currently underdeveloped. Here, a series of terpolymers copolymerized from two distinct organic comonomers and elemental sulfur yield polymers with a wide range of glass transition temperatures and show good mechanical properties.

Proton conduction is a fundamental process for fuel cell development, but three-dimensional proton conduction in crystalline porous solids is rare. Here, the authors report organic molecular cages in which the structure imposes three-dimensional proton conductivity competing with metal-organic frameworks.

Inverse vulcanization is a process that enables to convert sulfur, a by-product of the petroleum industry, into polymers. Here the authors report a synthetic method of inverse vulcanization via mechanochemical synthesis; compared to thermal routes, a broader range of monomers can be used, and the protocol yields materials with enhanced mercury capture capacity.

Energy–structure–function maps that describe the possible structures and properties of molecular crystals are developed, and these maps are used to guide the experimental discovery of porous materials with specific functions.

Organic molecular crystals with guest-occupied cavities are often observed, but the cavities tend to collapse when the guests are removed. Now, the porous domain of a crystalline solvate has been stabilized by formation of a cocrystal with a second molecule whose size and shape matches those of the unstable voids.

The surface areas of molecular organic cage solids now rival those of metal–organic frameworks. In this Review, the synthesis and structures of various porous organic cages are outlined together with a discussion of the characteristics — such as solubility, polymorphism and modular co-crystallization — that distinguish these cages from their inorganic or hybrid counterparts.