Multivariable Modular Design of Pore Space Partition

Pore space partition,
especially the one using C3-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 CO2 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.