Radical Polymerization of Vinyl Monomers in Porous Organic Cages

Abstract

The radical polymerization of vinyl monomers was performed in a tetrahedral imine-linked organic cage with extrinsic porosity (CC3). Because of its dynamic and responsive packing structure, CC3 endowed the polymerization with specific behaviors. The adsorption of styrene triggered a change in the CC3 assembly, resulting in a monomer arrangement that was suitable for polymerization within the host matrix. The polymerization reaction was strongly dependent on the crystallinity of CC3 and was promoted by amorphization of the host in a cooperative manner, which is not possible with conventional rigid porous materials. Furthermore, CC3 can recognize the polarity of substrates, and thus polar monomers, such as methyl methacrylate and acrylonitrile, could not induce the structural changes in CC3 that are required for polymerization. This monomer specificity governed by the flexibility of CC3 is useful to the prevent incorporation of unfavorable monomers into the polymeric products.

Iron Porphyrins Embedded into a Supramolecular Porous Organic Cage for Electrochemical CO2 Reduction in Water

“…POCs can possess large surface areas, exhibit high chemical stability, and be easily processed owing to their solubility . Advances in POC synthesis have enabled applications in host–guest chemistry, gas uptake and separation, nanoparticle synthesis, porous additives in materials, liquids, and cell membranes, as well as building blocks in extended frameworks and polymers …”

Direct Visualization of Pyrrole Reactivity upon Confinement within a Cyclodextrin Metal–Organic Framework

“…[21] Thei mpregnation and oxidative polymerization of pyrrole or thiophene is an effective strategy to endow insulating MOFs with extrinsic electrical conductivity,s imply by backfilling the pores with the conducting polymers generated in situ. [11,12,19,20,22] Oxidation generally leads to morphological damage that results in polycrystalline samples that are often amorphous.A saresult, previous works on extrinsically conductive MOFs make use of pressed pellets to collect electrical measurements.However,Rb-CD-MOF crystals are hundreds of micrometers wide and robust enough to withstand SCSC transformation and can be directly contacted to minimize the influence of grain boundaries in the conductivity measurements.T oi nvestigate the effect of short-range polymerization over the conductivity of the inclusion compound, we measured the electrical conductivity of Rb-CD-MOF, &Py,a nd &TPy single crystals by using at wo-probe contacts method (Figure 5a).…”

Direct Visualization of Pyrrole Reactivity upon Confinement within a Cyclodextrin Metal–Organic Framework

“…The impregnation and oxidative polymerization of pyrrole or thiophene is an effective strategy to endow insulating MOFs with extrinsic electrical conductivity, simply by backfilling the pores with the conducting polymers generated in situ . Oxidation generally leads to morphological damage that results in polycrystalline samples that are often amorphous.…”