Hf/porphyrin-based metal-organic framework PCN-224 for CO2 cycloaddition with epoxides

Abstract

Herein, we describe for the first time the synthesis of the highly porous Hf-tetracarboxylate porphyrinbased metal-organic framework (MOF) (Hf)PCN-224(M) (M ¼ H2, Co2þ). (Hf)PCN-224(H2) was easily and efficiently prepared following a simple microwave-assisted procedure with good yields (56e67%; spacetime yields: 1100e1270 kg m3 $day1 ), high crystallinity and phase purity by using trifluoromethanesulfonic acid and benzoic acid as modulators in less than 30 min. By simply introducing a preliminary step (10 min), 5,10,15,20-(tetra-4-carboxyphenyl)porphyrin linker (TCPP) was quantitatively metalated with Co2þ without additional purification and/or time consuming protection/deprotection steps to further obtain (Hf)PCN-224(Co). (Hf)PCN-224(Co) was then tested as catalyst in CO2 cycloaddition reaction with different epoxides to yield cyclic carbonates, showing the best catalytic performance described to date compared to other PCNs, under mild conditions (1 bar CO2, room temperature, 18 e24 h). Twelve epoxides were tested, obtaining from moderate to excellent conversions (35e96%). Moreover, this reaction was gram scaled-up (x50) without significant loss of yield to cyclic carbonates. (Hf)PCN-224(Co) maintained its integrity and crystallinity even after 8 consecutive runs, and poisoning was efficiently reverted by a simple thermal treatment (175 C, 6 h), fully recovering the initial catalytic activity.