A Stable Co(Ii)-Based Metal-Organic Framework With Dual-Functional Pyrazolate-Carboxylate Ligand: Construction And Co2 Selective Adsorption And Fixation

By taking the functional advantages of both pyrazolate and carboxylate ligands, a unique dual-functional pyrazolate-carboxylate ligand acid, 4-(3,6-di(pyrazol-4-yl)-9-carbazol-9-yl)benzoic acid (H(3)PCBA) was designed and synthesized. Using it, a new Co(II)-based metal-organic framework (MOF), Co-3(PC-BA)(2)(H2O)(2) (BUT-75) has been constructed. It revealed a (3,6)-connected net based on the 6-connected linear trinuclear metal node, and showed good chemical stability in a wide pH range from 3 to 12 at room temperature, as well as in boiling water. Due to the presence of rich exposed Co(II) sites in pores, BUT-75 presented high selective CO2 adsorption capacity over N-2 at 298 K. Simultaneously, it demonstrated fine catalytic performance for the cycloaddition of CO2 with epoxides into cyclic carbonates under ambient conditions. This work has not only enriched the MOF community through integrating diverse functionalities into one ligand but also contributed a versatile platform for CO2 fixation, thereby pushing MOF chemistry forward by stability enhancement and application expansion. (C) 2020 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.