One ligand, two roles: novel pillar-layered metal-organic frameworks built with a 3D ligand and asymmetric inorganic nodes.

Herein, we show two cases of pillar-layered MOFs which are built solely with one kind of three-dimensional (3D) ditopic ligand. The ligand in both structures functions not only as an intralayer linker in the layer but also as a "pillar" between adjacent layers. Such multi-functionality of the linker is accompanied by uncommon asymmetric 10- metal hexamer or 7- tetramer nodes, which have never been reported in previous 3D MOF structures.

Six-Membered Ring Directed Assembly of a Zirconium Zeolitic Metal-Organic Framework for Efficient Separation of Hexane Isomers.

The synthesis of zirconium MOFs with zeolite net is quite challenging due to the high connectivity of Zr clusters, which is far from tetrahedral connection, a requisite for zeolite net. In this work, we demonstrate a six-membered ring (6MR) strategy through mimicking of mineral zeolites with mixed ditopic and tritopic carboxylate linkers. With this strategy, the ditopic linker cross-links Zr clusters to form 4-connected zeolite-like nets, while the tritopic one is used to direct the formation of 6MR and simultaneously consumes extra coordination sites on the cluster.