Pore space partition, especially the one using C-symmetric 2,4,6-tri(4-pyridyl)-1,3,5-triazine as pore-partition agent in MIL-88 type (the acs net), has been shown to dramatically enhance CO uptake to near-record values. The continued advance in property engineering via pore space partition would depend on intelligent design of both framework components and pore-partition agent. Here, we report a new advance in the design of pore-partition agent by demonstrating a symmetry-guided pathway to develop a large variety of di- and trinuclear 1,2,4-triazolate-based clusters for use as pore-partition agent. The use of metal-organic clusters (instead of organic ligands) as pore-partition agent gives rise to many new pore-partitioned materials with huge compositional variety. The full assembly involves the simultaneous formation of two separate coordination architectures (i.e., the 3-D acs framework and 0-D triazolate clusters) and the eventual welding between the acs framework and triazolate clusters. The wide range of new compositions and structures provides a high degree of tunability in gas sorption properties.
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