Interpenetrating Metal–Metalloporphyrin Framework for Selective CO2 Uptake and Chemical Transformation of CO2

Herein we report a robust primitive cubic (pcu)-topology metal–metalloporphyrin framework (MMPF), MMPF-18, which was constructed from a ubiquitous secondary building unit of a tetranuclear zinc cluster, Zn4(μ4-O)­(−COO)6, and a linear organic linker of 5,15-bis­(4-carboxyphenyl)­porphyrin (H2bcpp). The strong π–π stacking from porphyrins and the lengthy H2bcpp ligand affords a 4-fold-interpenetrating network along with reduced void spaces and confined narrow channels. Thereby, MMPF-18 presents segmented pores and high-density metalloporphyrin centers for selective CO2 uptake over CH4 and size-selective chemical transformation of CO2 with epoxides forming cyclic carbonates under ambient conditions.