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Chemical and physical properties of porous solids are closely related to interactions between frameworks and guests in pores. The chemical environment of pores is highly tunable especially in metal-organic frameworks (MOFs). Thanks to rational structural design and rich choices of molecular building blocks, MOFs can accommodate multiple functional groups while the frameworks retain the backbone structures. Although the multivariate MOFs with various functionalized linkers showed novel properties, there is a still daunting challenge in understanding how diverse pore types are formed and controlling the pore population. In this poster presentation, we demonstrate, as an advanced multivariate platform, an isoreticular series of Zr-based metal-organic polyhedra (MOPs) with various combinations of functionalities (-H, -CH3, -NH2, -OH, -(CH3)2, -Br). A new synthetic method includes a mixed-cage strategy where the functionalized cages are mixed, compared with a mixed-linker strategy which yields a random distribution of functionalities (Figure). The clear differences in the cage population between mixed-linker and mixed-cage systems were observed in the mass spectra when the complexity increased from binary to senary mixing systems. This study highlights the potential of isoreticular MOPs for multiple functionalization and control of the component population, suggesting a new platform for emerging properties in multivariate porous solids.
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KCS