Solid-state materials formed from discrete imine macrocycles have potential in industrial separations, but dynamic behaviour during both synthesis and crystallisation makes them challenging to exploit. Here, we explore opportunities for structural control by investigating the dynamic nature of a C-5 brominated isotrianglimine in solution and under crystallisation conditions.

Supramolecular chemistry exploits non-covalent intramolecular interactions to form structures such as host-guest complexes and crystalline porous materials. Supramolecular materials have potential for applications in a future sustainable society, such as energy-efficient separation, pollution remediation, or energy storage, but their production frequently relies on unsustainable methods.

Here, we explore the use of Non-Thermal Plasma (NTP) as an efficient method for the synthesis of imine macrocycles at the gram scale. NTP-mediated macrocyclisations consistently achieved high yields of up to 97% in reduced reaction times compared to the standard non-plasma method, and were successfully carried out with a range of different aldehyde substrates.

Here, we use inexpensive calculations and high-throughput crystallisation experiments to identify accessible cage conformations for a recently reported organic cage by ‘locking’ them in the solid state. The conformers identified exhibit a range of distances between the carboxylic acid groups in the internal cavity, suggesting adaptability towards binding a wide array of target guest molecules.

Herein, we describe the crystal structures and gelation properties of a library of bis(urea) compounds and show, via molecular dynamics simulations, how gelator aggregation progresses from a continuous pattern of supramolecular motifs to a homogeneous fiber network.

Here, we explore the use of Non-Thermal Plasma (NTP) as an efficient method for the synthesis of imine macrocycles. NTP-mediated macrocyclisations consistently achieved high yields of up to 97 % in reduced reaction times compared to the standard non-plasma method, and were successfully carried out with a range of different aldehyde substrates.

Solid-state materials formed from discrete imine macrocycles have potential in industrial separations, but dynamic behaviour during both synthesis and crystallisation makes them challenging to exploit. Here, we explore opportunities for structural control by investigating the dynamic nature of a C-5 brominated isotrianglimine in solution and under crystallisation conditions.

High throughput screening was used to rapidly identify a new crystalline porous salt (CPOS). Using flow chemistry, the CPOS was scaled, and the material was shown to have permeant porosity with a carbon dioxide uptake of 4.3 mmol/g at 195 K, making it one of the most porous and scalable CPOS reported to date.

Porphyrin derivatives have found diverse applications due to their attractive photophysical and catalytic properties, but remain challenging to synthesize, particularly at scale. Porphyrin synthesis thus stands to benefit from the more controlled environment, opportunities for efficient optimization, and potential for scale-up available in flow.

A hydrogen-bonded framework that was predicted previously to have 3D porosity and a remarkably low density of 0.37 g cm−3 has been discovered experimentally. The structure of this framework matches the original prediction precisely and it has an accessible surface area of 3,284 m2 g−1, as measured by nitrogen adsorption, making it one of the most porous hydrogen-bonded frameworks synthesized to date.

Non-Thermal Plasma (NTP) is a promising state of matter for carrying out chemical reactions. NTP offers high densities of reactive species, without the need for a catalyst, while operating at atmospheric pressure and remaining at moderate temperature. Despite its potential, NTP cannot be used comprehensively in reactions until we understand more about the complex interactions of NTP and liquids.

Chemical recycling is one of the most promising technologies that could contribute to circular economy targets by providing solutions to plastic waste; however, it is still at an early stage of development. In this work, we describe the first light-driven, acid-catalyzed protocol for chemical recycling of polystyrene waste to valuable chemicals under 1 bar of O2.

Herein, we describe two isomeric macrocycles with clamp-like open and closed geometries, which crystallize as separate polymorphs but interconvert freely in solution. Using mechanistic information from NMR kinetic studies and at-line mass spectrometry, we developed a semicontinuous flow synthesis with maximum conversions of 85–93% and over 80% selectivity for a single isomer.

A combined experimental–computational approach enabled the synthesis of low-symmetry imine cages from mixtures of tetraaldehyde building blocks. This “social self-sorting” approach was applied to obtain a family of new cages containing heteroatoms, showing that pores of varying geometries and surface chemistries may be reliably accessed.

Methods to make microcapsules–used in a broad range of healthcare and energy applications–currently suffer from poor size control, limiting the establishment of size/property relationships. Here, we use microfluidics to produce monodisperse polyurea microcapsules (PUMC) with a limonene core.

Furocoumarin derivatives have been synthesized from single step, high yielding chemistry. They are characterized by FTIR, 1H-NMR, and, for the first time, a comprehensive UV-Vis and fluorescence spectroscopy study has been carried out to determine if these compounds can serve as useful sensors.

Here, we narrow the pore size of a cage molecule, CC3, in a systematic way by introducing methyl groups into the cage windows. Computational crystal structure prediction was used to anticipate the packing preferences of two homochiral methylated cages, CC14-R and CC15-R, and to assess the structure–energy landscape of a CC15-R/CC3-S cocrystal, designed such that both component cages could be directed to pack with a 3-D, interconnected pore structure.

Here we apply a chiral recognition strategy to a new family of tubular covalent cages to create both 1D porous nanotubes and 3D diamondoid pillared porous networks. These results are a blueprint for applying the ‘node and strut’ principles of reticular synthesis to molecular crystals.

The dynamic covalent synthesis of two imine-based porous organic cages was successfully transferred from batch to continuous flow. The same flow reactor was then used to scramble the constituents of these two cages in differing ratios to form cage mixtures. Preparative HPLC purification of one of these mixtures allowed rapid access to a desymmetrised cage molecule.

Three fluorescent organic compounds—furocoumarin (FC), dansyl aniline (DA), and 7-hydroxycoumarin3-carboxylic acid (CC)—are mixed to produce almost pure white light emission (WLE). This novel mixture is immobilised in silica aerogel and applied as a coating to a UV LED to demonstrate its applicability as a low-cost, organic coating for WLE via simultaneous emission.

In this work, the formation of nucleobase quartets consisting of adenine and thymine groups was used to control the 2D self-assembly of porphyrins.

Two dissymmetric racemic analogues of the chiral porous organic cage, CC3, were isolated and unambiguously characterised as a racemate pair of the R,R,R,S,S,S and S,S,S,R,R,R-diastereomers (CC3-RS and CC3-SR). CC3-RS/CC3-SR equals the highest porosity measured for CC3 but is an order of magnitude more soluble, making it an excellent candidate for incorporation into a membrane for separation applications.

Using variable temperature 2H static NMR spectra and 13C spin-lattice relaxation times (T1), we show that two different porous organic cages with tubular architectures are ultra-fast molecular rotors.

From kitchen sieves and strainers to coffee filters, porous materials have a wide range of uses. On an industrial scale, they are used as sorbents, filters, membranes, and catalysts. Slater and Cooper review how each application will limit the materials that can be used, and also the size and connectivity of the pores required. They go on to compare and contrast a growing range of porous materials that are finding increasing use in academic and industrial applications.