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Benzimidazolium-Decorated Metalloporphyrin Molecule and Polymer: a Reliable Preparation Method and Application in Catalyzing the Cycloaddition Reaction of CO2 and Epoxides |
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| Authors: | Dr. Yong Yang Qiang Wang Dr. Zhenping Su Prof. Jun Li Prof. Ning Wang |
| Affiliation: | 1. School of Chemistry and Materials Engineering, Huizhou University, Huizhou, 516007 P. R. China These authors contributed equally to this work. Contribution: Investigation (equal);2. Key Laboratory of Synthetic and Natural Functional Molecule of Ministry of Education College of Chemistry & Materials Science, Northwest University, Xi'an, 710069 P. R. China These authors contributed equally to this work. Contribution: Investigation (equal);3. School of Materials and Chemical Engineering, Yibin University, Yibin, 644000 P. R. China;4. Key Laboratory of Synthetic and Natural Functional Molecule of Ministry of Education College of Chemistry & Materials Science, Northwest University, Xi'an, 710069 P. R. China Contribution: Conceptualization (supporting);5. Key Laboratory of Synthetic and Natural Functional Molecule of Ministry of Education College of Chemistry & Materials Science, Northwest University, Xi'an, 710069 P. R. China |
| Abstract: | Due to the synergistic effect of central metal and halide anion, cationic metalloporphyrins and derivatives exhibit outstanding catalytic activities for the cycloaddition reaction of epoxides and carbon dioxide. Herein, a generic strategy was developed to synthesize the benzimidazolium-containing metalloporphyrin molecule and polymer. To demonstrate the method feasibility, we firstly synthesized the molecule 1H , in which the benzimidazole groups were in-site constructed by the cyclization of 5,10,15,20-(4-carboxyphenyl)-porphyrin ( H2TCPP ) with o-diaminobenzene ( PEA ). After post-synthetic ionization and metallization, I− and Zn2+ were introduced as the nucleophile and Lewis acid, respectively. The structure of 1ZnIL was confirmed by single crystal X-ray diffraction analysis. By using the similar conditions of model reaction, H2TCPP was copolymerized with 1,2,4,5-tetraaminobenzene ( BTA ) to prepare the polymer P-1ZnIL . The prepared cationic molecule 1ZnIL and polymer P-1ZnIL showed comparable activities in catalyzing the cycloaddition of carbon dioxide with epoxides to cyclic carbonates compared to the reported bifunctional catalysts based on metalloporphyrins. |
| Keywords: | benzimidazolium bifunctional catalyst CO2 cycloaddition metalloporphyrin oxygen heterocycles zinc |