Syntheses, Crystal Structures, and Gas Storage Studies in New Three-Dimensional 5-Aminoisophthalate Praseodymium Polymeric Complexes

The hydrothermal reaction of 5-aminoisophthalic acid and praseodymium oxide in different acids results in two new praseodymium coordination polymers, {Pr2(aip)3(H2O)2·3H2O}n (1) and {Pr2(Haip)2(aip)(NO3)2·8H2O}n (2) (aip = 5-aminoisophthalate). Complexes 1 and 2 are two distinct three-dimensional metal-organic frameworks constructed from the linkage of rod-shaped praseodymium carboxylate secondary building units and phenyl rings. Both dehydrated coordination frameworks are estimated using a computational method based on Connolly’s algorithm, indicating that dehydrated compound 1 cannot host molecules other than water molecules or He, whereas dehydrated compound 2 is able to host molecules with kinetic radii as big as 2.3 Å. The potential specific accessible surface of this compound is 792 m2 g−1. Meanwhile, N2 sorption measurements reveal that dehydrated compound 2 having a high 230 cm3/g (287 mg/g) N2 storage capacity at 77 K and 1 atm is in fairly good agreement with our calculation results. Moreover, powder X-ray diffraction measurement results demonstrated that the stable channels of dehydrated compound 2 can reversibly host other small solvent molecules (e.g., water, methanol, and ethanol) and grand canonical Monte Carlo simulation is applied to predict its hydrogen storage capacity.