Abstract
<h2>Summary</h2> 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.
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