Multivariable Modular Design of Pore Space Partition

Pore space partition, especially the one using C-3-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.