Porous aromatic framework with mesopores as a platform for a super-efficient heterogeneous Pd-based organometallic catalysis

A strategy using a mesoporous amine-tagged porous aromatic framework (PAF70-NH(2)) to immobilize a palladium (Pd)-based molecular catalyst has been developed. The resulting immobilized catalyst PAF70-Pd, in which the framework is entirely constructed by phenyl rings linked with stable carbon–carbon bonds, has high structural rigidity and stability. Compared with the known porous organic material immobilized Pd-based catalysts, PAF70-Pd has the highest Pd content so far. Moreover, PAF70-Pd has extremely high catalytic activity with good size selectivity and very easy recyclability in catalyzing the Suzuki–Miyaura coupling reaction. In the current system, the catalyst loading could be as low as 0.001 mol% and the TOF value could go up to 28 800 h(–1) which is far higher than those of the known porous organic material immobilized Pd-based catalysts. In order to elucidate the particularly high catalytic efficiency of PAF70-Pd, we prepared PAF1-Pd from PAF1-NH(2) for comparison. PAF1-Pd has a higher Pd content than PAF70-Pd. However, due to the absence of large enough mesopores in PAF1-NH(2), PAF1-Pd has almost no catalytic activity under the same conditions, which definitely demonstrated that the intrinsic mesoporosity of PAF70-NH(2) plays a crucial role in the superb catalytic efficiency of PAF70-Pd. This strategy to immobilize Pd-based molecular catalysts has very good expansibility to be applied in the immobilization of different organometallic catalysts into the pores of PAFs, which also has very high potential in the chemical and pharmaceutical industry.