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A facile and one-pot synthesis of metalloporphyrin-based ionic porous organic polymers (M-iPOPs) was performed through a typical Yamamoto-Ullmann coupling reaction for the first time. We used various characterization techniques to demonstrate that these strongly polar Al-based materials (Al-iPOP) possessed a relatively uniform microporosity, good swellable features, and a good CO capture capacity. If we consider the particular physicochemical properties, heterogeneous Al-iPOP, which bears both a metal active center and halogen anion, acted as a bifunctional catalyst for the solvent- and additive-free synthesis of cyclic carbonates from various epoxides and CO with an excellent activity and good recyclability under mild conditions. Interestingly, these CO -philic materials could catalyze the cycloaddition reaction smoothly by using simulated flue gas (15 % CO in N , v/v) as a raw material, which indicates that a stable local microenvironment and polymer swellability might promote the transformation. Thus, the introduction of polar ionic liquid units into metalloporphyrin-based porous materials is regarded as a promising new strategy for the chemical conversion of CO .

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Multifunctionalization of organic polymers for acting synergistically on substrate is of wide interest in the field of modern catalysis, but it is still a significant challenge. Herein, two novel bifunctional polymers were first designed and synthesized by combining ionic liquids (ILs) with zinc(II) porphyrin through simple and reversible Schiff base reactions. The fabricated polymers with flexible structures and nitrogen-rich environments presented high affinity toward CO 2 molecules at ambient conditions. Owing to the cooperative nature of intercalated ILs and Lewis acidic metal sites, these materials could serve as efficient heterogeneous catalysts for the insertion of CO 2 into epoxides to produce cyclic carbonates. As expected, these polymers exhibited good catalytic performance, robust constancy, excellent recyclability, and good substrate expansibility for this reaction in the absence of cocatalyst under mild or even ambient conditions. Notably, the selected catalyst SYSU-Zn@IL2 could directly convert diluted CO 2 (15% CO 2 in N 2 ) into cyclic carbonate at 80 °C and 3.0 MPa, further offering the great application potential for recycling real-world carbon resource.

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Based on the concept of function-oriented synthesis, we pertinently developed a series of new functional ionic polymers, which exhibited good catalytic performance, robust constancy, and excellent substrate expansibility for sustainable catalysis of CO2-involved reactions.

Using concepts of biomimetic catalysis, a kind of tin porphyrin-based porous aromatic framework (SnPor@ PAF) with broad and strong optical absorption in the visible light region was successfully synthesized and subsequently used in the aerobic oxidation of sulfides to sulfoxides under ambient conditions and visible light irradiation, in which exhibited enzyme-like features of high efficiency and high selectivity.More interestingly, heterogeneous SnPor@PAF was naturally regarded as an intriguing and versatile photosensitizer for photocatalytic transformation and could be reused several times because of its robust and rigid porphyrin framework. As expected, their p-conjugated structure characteristic in the molecular skeleton might facilitate the activation of molecular oxygen under mild reaction conditions and promoted the production of reactive oxygen species (singlet oxygen ( 1 O 2 ) and superoxide radical anion (O 2 *À )), which would involve energy transfer and/or electron transfer process. Experimental investigations including emission quenching experiment, oxygen-isotope labelling, typical inhibition experiments, classical fluorescence probe study, photo-oxidation of a-terpinene and in situ electron spin resonance, could provide a mechanistic insight into the photocatalytic reactions.

The zinc(ii) complexes containing the rigid N-chelating ligand proved to be highly efficient and bi-functional catalysts towards the synthesis of cyclic carbonate from epoxide and CO2 without the use of any co-catalyst or organic solvent.