Linker Dimensionality Regulation Enabled Isoreticular Extension in Copper-Based Metal-Organic Frameworks for Enhanced CO2 Adsorption and Hydrocarbon Separation.

Isoreticular extension of metal-organic frameworks (MOFs) has proven to be a powerful strategy for targeting appropriate pore shapes and sizes suitable for specific applications while retaining the underlying net topology. However, this strategy can be limiting due to the tendency of elongated linkers to result in completely new topologies. The formulation of linker design principles that govern the isoreticular extension is crucial for decoding the relationships between the linker dimensionality and the MOF topologies. In this work, capitalizing on typical tritopic linkers, we designed and synthesized an anthracene-embedded linker for systematically investigating the role of linker dimensionality in manipulating MOF topology. The anthracene-extended linker, in contrast to the benzene-extended analogue, leads to a Cu-MOF (SJTU-150) with prototypical agw topology, which is the same as the Cu-MOFs built from shortened linkers. The different MOF topologies observed in the benzene- and anthracene-extended linkers underscore the importance of linker dimensionality engineering in isoreticular chemistry. SJTU-150 featuring multianthracene-functionalized pores shows high affinity toward CO2 and demonstrates potential in natural gas upgrading. This work thus provides a molecular insight of leveraging linker dimensionality to enable isoreticular extension in MOFs and underscores the unique role of the anthracene moiety in the enhancement of gas adsorption properties.