An antiferromagnetic metalloring pyrazolate (Pz) framework with [Cu12(μ2-OH)12(Pz)12] nodes for separation of C2H2/CH4 mixture

The search for functional metalloring organic frameworks (MROFs) has been of continuous interest in the fields of both molecular rings and metal-organic frameworks (MOFs) due to their importance in many multifunctional applications. Herein, a hierarchical pyrazolate framework MROF-12 with the topology of the Schlafli symbol {4(60).6(6)} is reported, which is constructed by an elongated rigid ligand and attractive metalloring cluster nodes [Cu-12(mu(2)-OH)(12)(Pz)(12)]. MROF-12 not only adopts the unique functionalities of the metalloring clusters but also inherits the porous properties of MOFs. The large [Cu-12(mu(2)-OH)(12)(Pz)(12)] metalloring nodes with the diameter of 12.202 angstrom endow MROF-12 with excellent stability and antiferromagnetism, and they are bridged by linear pyrazolate ligands (H2NDI) to form micro-mesoporous MROF with permanent porosity. The activated sample MROF-12a can exhibit a relatively high Brunauer-Emmett-Teller/Langmuir surface area (460.7/571.9 m(2) g(-1)) as well as pore volume of 0.240 cm(3) g(-1). Dynamic fixed bed breakthrough experiments indicate that the separation of C2H2/CH4 or CO2/CH4 mixtures can be efficiently achieved through a column packed with MROF-12a solid.