Multivariate porous platform based on metal-organic polyhedra with controllable functionality assembly

The chemical environment of pores is important for various applications of porous solids. Thanks to reticular chemistry, metal organic frameworks (MOFs) have become a versatile platform targeting numerous applications through multiple functionalizations. Although multivariate MOFs often display novel properties, identifying and manipulating pore types remain a daunting challenge. Here, we present an isoreticular series of Zr-based metal-organic polyhedra (MOPs) as a porous platform to achieve controllable intrinsic pores. Two multivariate synthetic approaches were demonstrated: a mixed-cage strategy, whereby functionalized cages are mixed, compared with the conventional mixed-linker strategy, which yields a random distribution of functionalities. A remarkable difference in functionality assembly was achieved between the strategies, with complexity increasing from binary to senary systems. More interestingly, distinct photophysical properties were observed between mixed-linker and mixed-cage samples and attributed to radiative decay kinetics. This study highlights the potential of MOPs as a unique multivariate platform with tunable component assembly to study the emerging properties of multivariate porous solids.

Automated summary

The chemical environment of pores is crucial for various applications of porous solids, and metal-organic polyhedra (MOPs) based on Zr have been shown to be a versatile platform with controllable intrinsic pores. By utilizing mixed-cage and mixed-linker synthesis approaches, different levels of complexity in functionality assembly can be achieved. This study demonstrates the potential of MOPs as a unique multivariate platform for studying the emerging properties of multivariate porous solids.