A new generation of confined palladium(II) catalysts covalently attached inside of porous organic polymers (POPs) has been attained. The synthetic approach employed was straightforward, and there was no prerequisite for making any modification of the precursor polymer. First, POP-based catalytic supports were obtained by reacting one symmetric trifunctional aromatic monomer (1,3,5-triphenylbenzene) with two ketones having electron-withdrawing groups (4,5-diazafluoren-9-one, DAFO, and isatin) in superacidic media. The homopolymers and copolymers were made using stoichiometric ratios between the functional groups, and they were obtained with quantitative yields after the optimization of reaction conditions. Moreover, the number of chelating groups (bipyridine moieties) available to bind Pd(II) ions to the catalyst supports was modified using different DAFO/isatin ratios. The resulting amorphous polymers and copolymers showed high thermal stability, above 500 °C, and moderate-high specific surface areas (from 760 to 935 m² g^-1), with high microporosity contribution (from 64 to 77%). Next, POP-supported Pd(II) catalysts were obtained by simple immersion of the catalyst supports in a palladium(II) acetate solution, observing that the metal content was similar to that theoretically expected according to the amount of bipyridine groups present. The catalytic activity of these heterogeneous catalysts was explored for the synthesis of biphenyl and terphenyl compounds, via the Suzuki-Miyaura cross-coupling reaction using a green solvent (ethanol/water), low palladium loads, and aerobic conditions. The findings showed excellent catalytic activity with quantitative product yields. Additionally, the recyclability of the catalysts, by simply washing it with ethanol, was excellent, with a sp²-sp² coupling yield higher than 95% after five cycles of use. Finally, the feasibility of these catalysts to be employed in tangible organic reactions was assessed. Thus, the synthesis of a bulky compound, 4,4'-dimethoxy-5'-tert-butyl-m-terphenylene, which is a precursor of a thermal rearrangement monomer, was scaled-up to 2 g, with high conversion and 96% yield of the pure product.

	Year	Citations

About