Design of novel bilayer compounds of the CPO-8 type containing 1D channels

The reaction between Zn(NO3)center dot 6H(2)O and 5-aminoisophthalic acid (aip) in a mixture of diethylformamide (DEF) and ethanol resulted in [Zn(C8H5NO4)(C5H11NO)](n) (CPO-8-DEF). This compound is composed of infinite 2D layers with tetrahedral Zn atoms and aip ligands in a triangular topology. The DEF molecules are bonded to Zn, and within each layer, the DEF molecules are oriented in the same direction, while in the subsequent layer, the DEF molecules are oriented in the opposite direction. By introduction of the pillaring ligands 4,4-bipyridine (BPY), 1,2-di-4-pyridylethylene (DIPE), 1,2-di-4-pyridylethane (DPA), and 1,3-di-4-pyridylpropane (DIPP) into mixtures of N,N-dimethylformamide and water with Zn(NO3)(2) and aip, we have successfully synthesized a series of related pillared bilayer compounds with the same common triangular Zn(aip) layer structural motif as that observed in CPO-8-DEF. The compounds are denoted as CPO-8-BPY ([Zn(C8H5NO4)(ClOH8N2)(0.5)]center dot 3nH(2)O), CPO-8-DPE ([Zn(C8H5NO4)(Cl2H10N2)(0.5)](n)center dot 2.5nH(2)O), CPO-8-DPA ([Zn(C8H5NO4)(Cl2H12N2)(0.5)](n)center dot 2.5nH(2)O), and CPO-8-DPP ([Zn(C8H5NO4)(C13H14N2)(0.5)](n)center dot 3nH(2)O), In all cases, the pillars create spaces inside the bilayers that result in 1 D channels running along the [010] directions with dimensions of 3.5 x 6.7 angstrom(2). These channels contain water molecules that can be removed on heating to 150 degrees C, resulting in porous structures. The crystal structures of these porous high-temperature variants have been determined on the basis of powder X-ray diffraction data. All of the compounds show preferential adsorption of H-2 over N-2 at 77 K.