The advent of conjugated microporous polymers (CMPs) has had significant impact in catalysis. However, the presence of only micropores in these polymers often imposes diffusion limitations, which has resulted in the low utilization of CMPs in catalytic reactions. Herein, the preparation of a foam-supporting CMP composite with interconnective micropores and macropores and elastic properties is reported. Metalloporphyrin-based CMP organogels are synthesized within the melamine foam by a room-temperature oxidative homocoupling reaction of terminal alkynes. Upon drying, the CMP-based xerogels tightly wrap the framework skeletons of the foam, while the foam cells are still open to allow for the preservation of elasticity and macroporosity. Such a hierarchical structure is efficient for acyl transfer, facilitates substrate diffusion within interpenetrative macropores and micropores, and could be used to intensify catalytic processes.

No abstract

A two-step polymerization combining miniemulsion and solvothermal techniques was applied to synthesize tetraphenylethene-based nanoscale conjugated microporous polymers (TPE-NCMP), which simultaneously possessed a large surface area (1214 m 2 /g) and a high aggregation-induced florescence quantum yield (58%). Immobilization of Nile Red within micropores of TPE-NCMPs constructed a light-harvesting composite with characteristics of intense photons acquisition and efficient energy migration. Homogenous NCMP-based films were fabricated by blending the dye-doped TPE-NCMPs with PVA. The fluorescence emission could be flexibly tuned by varying the dosage of dyes over the whole visible spectrum including a pure white light.

Metalloporphyrin-based CMP nanoparticles synthesized by the oxidative dimerization of terminal alkynes in the toluene-in-water miniemulsion possess native porosity, outstanding solution processability and uniform nanosized distribution. Also, they exhibit the sensitive color-switching ability for quantitative assay of gaseous SO2 by the noncovalent complex-displacement reaction at liquid-solid or gas-solid interfaces.

A Pd­(II)/Cu­(I) cocatalyzed homocoupling reaction of terminal alkynes to diynes was used to synthesize conjugated polymer organogels with tetragonal topological frameworks consisting of Zn-porphyrin units as nodes and diynes as struts. This material appears fibrous with a micrometer length, possesses outstanding elastic properties, and could be organized into desired modules. Upon drying, the transformed xerogels afford superior thermal stability and microporosity, implying that they are supported by conjugated microporous polymer (CMP) skeletons at the molecular level. The microporosity of CMP-structured xerogels could be adjusted by varying the monomer concentrations, reaction temperatures and solvent species. The notable narrowed pore size distribution is achieved under optimal conditions, which results in CMP-supported xerogels outperforming the most reported CMPs, although the networks are still amorphous in nature. By following the same synthesis route, for the first time, the interpenetrating polymer network organogels were prepared by forming two CMP components sequentially in a temperature-controlled manner and in one pot. This provides an unprecedented combination of multiple interwoven CMP modules whose functions could be assembled synergistically for prospective broader applications.