Reconciling the Discrepancies between Crystallographic Porosity and Guest Access As Exemplified by Zn-HKUST-1

There are several compounds for which there exists a disconnect between porosity as predicted by crystallography and porosity measured by gas sorption analysis. In this paper, the Zn-based analogue of Cu-3(btc)(2) (HKUST-1), Zn-3(btc)(2) (Zn-HKUST-1; btc = 1,3,5-benzenetricarboxylate) is investigated. Conventional analysis of Zn-HKUST-1 by powder X-ray diffraction and gas sorption indicates retention of crystalline structure but negligible nitrogen uptake at 77 K. By using positron annihilation lifetime spectroscopy, a densified surface layer preventing the entry of even small molecular species into the crystal framework is revealed. The material is shown to have inherent surface instability after solvent removal, rendering it impermeable to molecular guests irrespective of handling and processing methods. This previously unobserved surface instability may provide insight into the failure of other microporous coordination polymers to exhibit significant porosity despite crystal structures indicative of regular, interconnected, microporous networks.