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In this work, metalloporphyrins‐based MOGs were synthesized as precursor to prepare porous coordination polymers (PCPs). Firstly, the carboxyl metalloporphyrins MCPp (M = Zn (II), Co (II), Cu (II), Mn (III)OAc; CPp = 5,10,15,20‐tetra(4‐(3‐carboxy)phenoxy)phenylporphyrin) were synthesized as gelator. Then, the metalloporphyrin‐based MOGs were prepared with MCPp and Al(NO3)3·9H2O by sol–gel method. Moreover, the residual reactants and solvent molecules in MOGs were removed by Soxhlet extraction and supercritical CO2 extraction to get the finial porous coordination polymers. This methodology effectually avoids the collapse of frame construction. Compared with the reference material prepared by the oven‐dry method, these PCPs exhibit much higher BET surface ranging from 398 to 439 m2 g−1. The PCPs were carefully characterized by FT‐IR, UV–vis, SEM, TEM and PXRD, and exhibit excellent catalytic activities and stabilities for the oxidation of ethylbenzene. [ABSTRACT FROM AUTHOR]

Two carboxyl‐functional Mn (III)–porphyrins reacted with two metal nitrates (Cr (NO3)3·9H2O and Al (NO3)3·9H2O) via solvothermal method, respectively, to produce four metalloporphyrin‐based metal organic gels (MOGs). To remove unreacted metal salts and DMF, the gels were dealt with Soxhlet extraction and supercritical CO2. Finally, four desired porous coordination polymers (PCPs) were prepared. The newly synthesized PCPs were characterized by FT‐IR, UV–vis, SEM, and TEM. The contrast experiments show these PCPs possess good catalytic activities for the cycloaddition reactions of epoxide and CO2 under mild and solvent‐free conditions using tetrabutylammonium bromide (TBAB) as co‐catalyst. [ABSTRACT FROM AUTHOR]

The design and synthesis of efficient heterogeneous catalysts for catalytic conversion of CO2 are an important challenge. The novel zinc porphyrin polymer reported herein, [ZnPy+CPP‐BTA]I−, is synthesized from trans‐A2B2 porphyrin precursor 5,15‐(4‐carboxyphenyl)‐10,20‐(pyridyl)‐porphyrin (PyCPP) and 1,2,4,5‐benzenetetramine tetrahydrochloride (BTA), employing a sequential post‐synthetic methylation and metalation strategy. The newly synthesized zinc porphyrin polymer was well characterized by Fourier transform infrared spectroscopy (FT‐IR), Ultraviolet–visible spectroscopy (UV–vis), scanning electron microscope (SEM), transmission electron microscope (TEM), thermal gravimetric analysis (TGA), and X‐ray photoelectron spectroscopy (XPS). As bifunctional heterogeneous catalyst incorporated zinc porphyrin and nucleophile I−, [ZnPy+CPP‐BTA]I− shows good catalytic activity and recyclability for the cycloaddition reactions of epoxides and CO2 under lower CO2 initial pressure and cocatalyst‐free conditions. [ABSTRACT FROM AUTHOR]