Catalysis by microporous phthalocyanine and porphyrin network polymers

Cobalt phthalocyanine and iron porphyrin network polymers of intrinsic microporosity (network-PIMs) were prepared and their performance as heterogeneous catalysts compared with that of low molar mass analogues. Spiro-linked Co phthalocyanine network-PIMs prepared from preformed chlorinated phthalocyanines showed lower surface areas and lower catalytic activity than those prepared by a phthalocyanine-forming reaction from a rigid precursor incorporating a spiro-centre. However, all the phthalocyanine network-PIMs were much more effective catalysts than low molar mass Co phthalocyanine for the decomposition of hydrogen peroxide, the oxidation of cyclohexene and the oxidation of hydroquinone. An Fe porphyrin network-PIM showed a higher surface area than any of the phthalocyanine polymers and showed higher activity for the oxidation of hydroquinone, also outperforming a low molar mass FeCl porphyrin.