rystalline covalent organic frameworks (COFs) have received much attention because of their use in catalysis, adsorption, separation, chemosensing, drug delivery and energy storage and production [1][2][3] . The traditional route to COFs is solvothermal synthesis 4 , but this often requires the use of sealed, pressurized tubes, elevated reaction temperatures (120-200 °C), long reaction times (2-7 days) and toxic organic solvents. These drawbacks provide an incentive to develop alternative methods to synthesize COFs.Alternatives to solvothermal syntheses include microwave synthesis 5 and room-temperature syntheses using catalysts 6,7 . These routes can be much faster than solvothermal syntheses, with reaction times of 1-2 h. However, it is still desirable to avoid the use of toxic organic solvents and metal catalysts. Solid-state synthesis is one route that eliminates bulk solvent use and reduces waste generation. p-Toluenesulfonic acid, a strong solid acid, was first used as the catalyst for solid-state COF synthesis by Kandambeth et al. 8 . However, a large quantity of p-toluenesulfonic acid (~6 molar equiv. based on the amine monomers) was required during the synthesis, and high temperatures (90-170 °C) for one minute to two days were needed to obtain the crystalline COFs 9,10 . Mechanochemical synthesis is another promising solid-state route. The first examples of COF mechanosynthesis were reported by Biswal et al. 11 . Solvent-free mechanochemical processes offer the potential for large-scale COF synthesis, but such studies are rare and the COFs produced have limited crystallinity and porosity 12 . For example, the mechanically synthesized COFs TpPa-1, TpPa-2 and TpBD had only moderate crystallinity and low Brunauer-Emmet-Teller (BET) surface areas (61 m 2 g -1 for TpPa-1, 56 m 2 g -1 for TpPa-2 and 35 m 2 g -1 for TpBD) compared with those of their solvothermal analogues 11 . Recent work by Emmerling et al. 13 showed that alternative activation methods, such as supercritical CO 2 drying 14,15 , may allow access to the porosity of mechanochemically prepared COFs.

Sulfonated hyper-cross-linked polymers based on 4,4′-bis­(chloromethyl)-1,1′-biphenyl (BCMBP) were synthesized via metal-free (SHCP-1) and conventional Lewis acid-catalyzed (SHCP-2) Friedel–Crafts alkylation routes. The sulfonated polymers possessed BET surface areas in excess of 500 m2·g–1. SHCP-1 was investigated for its ability to extract Sr and Cs ions from aqueous solutions via the ion-exchange reaction of the sulfonic acid moiety. Equilibrium uptake data could be accurately modeled by the Dubinin–Radushkevich isotherm, with maximum calculated loading values of 95.6 ± 2.8 mg·g–1 (Sr) and 273 ± 37 mg·g–1 (Cs). Uptake of both target ions was rapid, with pseudo second-order rate constants calculated as 7.71 ± 1.1 (×10–2) for Sr and 0.113 ± 0.014 for Cs. Furthermore, the polymer was found to be highly selective toward the target ions over large excesses of naturally occurring competing metal ions Na, K, Mg, and Ca. We conclude that hyper-cross-linked polymers may offer intrinsic advantages over other adsorbents for the remediation of aqueous Sr and Cs contamination.

Dispersible microporous polymer nanoparticles formed via the RAFT-PISA polymerisation of divinylbenzene and fumaronitrile using a PEG macro-CTA.

A dispersible porous polymer (PEG113‐b‐DVB800‐co‐AA200) based on the controlled radical polymerization of divinylbenzene and acrylic acid with a poly(ethylene glycol) (PEG) macrochain transfer agent (macro‐CTA) is synthesized and postsynthetically modified with anthracene. This blue‐emitting porous polymer is used to encapsulate the yellow‐emitting fluorophore rhodamine B into its core, resulting in a white‐light emitting dispersion with a quantum yield of 38% and commission internationale de l’éclairage coordinates of (X = 0.33, Y = 0.32).

The methanol carbonylation catalyst, cis-[Rh(CO)2I2]–, has been heterogenised within a dispersible microporous polymer support bearing cationic functionality. The microporous polymer has a core-shell structure in which the porous and insoluble...

The first metallated hypercrosslinked polymers have been synthesised, characterised and found to have remarkable capacity for uptake of fluoride ions.

A porous molecular crystal (TSCl) was found to crystallize from dichloromethane and water during the synthesis of tetrakis(4-sulfophenylmethane). Crystal structure prediction (CSP) rationalizes the driving force behind the formation of...

<p>Water-dispersible porous polymeric dispersions (PPDs) have been synthesised by reversible addition-fragmentation chain transfer mediated polymerisation-induced self-assembly (RAFT-mediated PISA). The core-shell particles posses a microporous core formed from divinylbenzene and fumaronitrile while the outer polyethylene glycol shell enables the particles to be dispersible in a wide range of solvents. The PPD was shown to have a heirarchical structure of small primary nanoparticles within larger, well-defined aggregates of 220 nm as measured by electron microscopy and small angle x-ray scattering (SAXS) and exhibited a surface area of 274 m²/g. Furthermore these samples were found to be fluoresent and demonstrate selective detection of harmful nitroaramatics in solution with extremly low limits of detection, 169 ppb for picric acid, as well as possessing a CO₂ uptake of 1.1 mmol/g at 273 K.</p>