Delocalized electron effect on single metal sites in ultrathin conjugated microporous polymer nanosheets for boosting CO2 cycloaddition

Xiaofei Zhang*, Haitao Liu, Pengfei An, Yanan Shi, Jianyu Han, Zhongjie Yang, Chang Long, Jun Guo, Shenlong Zhao, Kun Zhao, Huajie Yin, Lirong Zheng, Binhao Zhang, Xiaoping Liu, Lijuan Zhang*, Guodong Li*, Zhiyong Tang*
Science Advances 6(17), eaaz4824, (2020)


CO2 cycloaddition with epoxides at low temperature and pressure has been broadly recognized as an ambitious but challenging goal, which requires the catalysts to have precisely controlled Lewis acid sites. Here, we demonstrate that both stereochemical environment and oxidation state of single cobalt active sites in cobalt tetraaminophthalocyanine [CoPc(NH2)4] are finely tuned via molecular engineering with 2,5-di-tert-butyl-1,4-benzoquinone (DTBBQ). Notably, DTBBQ incorporation not only enables formation of 5-nm-thick conjugated microporous polymer (CMP) nanosheets due to the steric hindrance effect of tert-butyl groups but also makes isolated cobalt sites with high oxidation state due to the presence of delocalized electron-withdrawing effect of alkene groups in DTBBQ via conjugated skeleton. Notably, when used as heterogeneous catalysts for CO2 cycloaddition with different epoxides, single cobalt active sites on the ultrathin CMP nanosheets exhibit unprecedentedly high activity and excellent stability under mild reaction conditions.