A metalloporphyrin-based porous organic polymer, Mn-PPOP-1, was constructed in high yield via the ketoenamine condensation of robust porphyrin tetraamines (TBPP) with 1,3,5-triformylphloroglucinol. The stable keto-enamine form in the synthesized polymer was unambiguously confirmed by C CP-MAS solid state NMR. Noticeably, besides the high thermal and chemical stability, this material contains both micropores and mesopores, which are favorable for mass transfer in the catalytic application. Mn-PPOP-1 exhibits significantly high catalytic oxidation of olefins and arylalkanes at room temperature. The catalytic activity and stability of Mn-PPOP-1 are apparently superior to those of the homogeneous manganese porphyrins. These results indicate that the metalloporphyrin-based porous organic polymer is a promising candidate for efficient heterogeneous catalysts.

A hexagonal porphyrin-based porous organic polymer, namely, CPF-1, was constructed by 3+2 ketoenamine condensation of the C -symmetric porphyrin diamine 5,15-bis(4-aminophenyl)-10,20-diphenylporphyrin and 1,3,5-triformylphloroglucinol. This material exhibits permanent porosity and excellent thermal and chemical stability. CPF-1 can be employed as a superior supporting substrate to immobilize Au nanoparticles (NPs) as a result of the strong interactions between Au NPs and the CPF support. An Au@CPF-1 hybrid was synthesized by an interfacial solution infiltration method with NaBH as reducing agent. Au NPs (5 nm) grew on CPF-1 and were distributed without aggregation. Moreover, Au@CPF-1 exhibits superior catalytic activity compared to many other reported Au-based catalysts for the reduction of 4-nitrophenol in the presence of NaBH . In addition, Au@CPF-1 has excellent stability and recyclability, and it can be reused for three successive reaction cycles without loss of activity. The dense distribution of phenyl rings on the channel walls of the CPF support can reasonably be regarded as the active sites that adsorb the 4-nitrophenol molecule through hydrogen-bonding and C-H⋅⋅⋅π interactions, as was confirmed by the X-ray structure of model compound DAPP-Benz.

The first SCO@SCO core-shell nanomaterials have been synthesized by the step-by-step microemulsion method. The observed gyroscopic core-shell nanocomposites exhibit three-step spin crossover behaviour with thermal hysteresis at around room temperature. This offers an efficient and novel strategy for the development of multistable SCO materials.