Cao Qiang, Yin Qing, Chen Qi, Dong Zhi-Bing, Han Bao-Hang
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing, 100190, P.R. China.
School of Chemistry and Environmental Engineering, Wuhan Institute of Technology, Wuhan, 430074, P.R. China.
Chemistry. 2017 Jul 21;23(41):9831-9837. doi: 10.1002/chem.201700916. Epub 2017 Jun 27.
By considering the high reactivity of fluorinated iron-porphyrin and good stability of porphyrin-based porous polymers, fluorinated iron-porphyrin conjugated porous polymers (FPOP-3-6) were synthesized through direct C-H arylation polymerization. The obtained materials are chemically and thermally stable, of which FPOP-3 exhibits the highest Brunauer-Emmett-Teller specific surface area (about 840 m g ). For functional studies of the obtained polymers as heterogeneous catalysts, catalytic transformation of cycloketones into lactones by oxygen through Baeyer-Villiger oxidation was used as a model reaction. Fluorinated phenyl substituents of the iron-porphyrin not only are beneficial to the conversion, but also can stabilize the porphyrin to resist catalyst breakdown. The polymer FPOP-3, with high porosity, exhibits the best catalytic efficiency and recycling effect. The recovered catalyst also shows good catalytic activities after recycling three times with a small loss in yield.
考虑到氟化铁卟啉的高反应活性以及卟啉基多孔聚合物的良好稳定性，通过直接C-H芳基化聚合反应合成了氟化铁卟啉共轭多孔聚合物（FPOP-3-6）。所获得的材料具有化学和热稳定性，其中FPOP-3表现出最高的布鲁诺尔-埃米特-特勒比表面积（约840 m²/g）。为了对所获得的聚合物作为多相催化剂进行功能研究，以通过拜耳-维利格氧化反应将环酮通过氧气催化转化为内酯作为模型反应。铁卟啉的氟化苯基取代基不仅有利于转化，还能稳定卟啉以抵抗催化剂分解。具有高孔隙率的聚合物FPOP-3表现出最佳的催化效率和循环效果。回收的催化剂在循环使用三次后仍显示出良好的催化活性，产率仅有少量损失。
