Adsorbate-dependent phase switching in the square lattice topology coordination network [Ni(4,40 -bipyridine)2(NCS)2]n

Switching coordination networks (CNs) featuring stepped sorption isotherms that are accompanied by phase changes offer promise for gas storage and separation applications. However, their responsiveness to different adsorbates remains largely understudied. Herein, we report the variable switching behaviour of a previously known square lattice (sql) topology CN, [Ni(4,4′-bipyridine)2(NCS)2] (sql-1-Ni-NCS), with respect to nine gaseous adsorbates.</p

The impact of solution vs. slurry vs. mechanochemical syntheses upon the sorption performance of a 2D switching coordination network

The selection and optimization of synthesis routes for porous metal–organic materials are critical for their large-scale manufacture but remain largely underexplored. In this study, we compare mechanochemistry vs. slurry vs. solution methods for the synthesis of a 1D chain coordination polymer {[Co(bpy)(NCS)2(H2O)2]·bpy}n (chn-1-Co-NCS-H2O) that is an intermediate to the 2D switching coordination network [Co(bpy)2(NCS)2]n, sql-1-Co-NCS (1 = bpy = 4,4′-bipyridine). Although neat mechanosynthesis using Co(NCS)2 and bpy as the starting materials failed, both water slurry and water-assisted mechanochemical syntheses afforded the desired intermediate, chn-1-Co-NCS-H2O, in high yield. Nevertheless, the resulting sql-1-Co-NCS products were observed to exhibit different CO2 sorption profiles depending on the synthesis methods used to prepare chn-1-Co-NCS-H2O. This study reveals that water can play an important role in mechanosynthesis, not only by inducing and accelerating the reaction process, but also by enhancing product quality in a manner that is not readily detectable by PXRD.</p

Pressure-induced structural effects in the square lattice (sql) topology coordination network Sql-1-Co-NCS·4OX

A high-pressure study of a switching coordination network of square lattice topology (sql) loaded with o-xylene (OX), [Co(4,4′-bipyridine)2(NCS)2]n·4nC8H10 (sql-1-Co?NCS·4OX), was conducted up to approximately 1 GPa to investigate pressure-induced structural changes. Previous reports revealed that sql-1-Co-NCS exhibits multiple phases thanks to its ability to switch between closed (nonporous) and several open (porous) phases in the presence of various gases, vapors, and liquids. Networks of such properties are of topical interest because they can offer high working capacity and improved recyclability for gas adsorption. The monoclinic crystal structure of sql-1-Co-NCS·4OX at 100 K was previously reported to show an increase in interlayer separation of more than 100% compared to the corresponding closed phase, sql-1-Co-NCS, when exposed to gases or vapors under ambient conditions. Herein, a tetragonal crystal form of sql-1-Co-NCS·4OX (space group I4/mmm, Phase I) that exists at 0.1 MPa/303 K is reported. Exposure of Phase I to high pressure using penetrable pressure transmitting media (OX and 1:1 vol MeOH/EtOH) did not result in further separation of the sql networks. Rather, compression of the crystals and release of adsorbed OX molecules occurred. These pressure-induced changes are discussed in terms of structural voids, framework conformation, and molecular packing of the sql layers. Although Phase I retained tetragonal symmetry throughout the investigated pressure range, the interlayer voids occupied by OX molecules were significantly reduced between 0.3 and 0.5 GPa; further compression above 0.5 GPa induced structural disorder. Additionally, analysis of the electron count present in the pores of sql-1-Co-NCS confirmed the multistep evacuation of OX molecules from the crystal, and two intermediate phases, Ia and Ib, differing in the OX loading level, are postulated </p

Water vapour and gas induced phase transformations in an 8-fold interpenetrated diamondoid metal–organic framework

In this work, we report the synthesis, structural characterisation and sorption properties of an 8-fold interpenetrated diamondoid (dia) metal–organic framework (MOF) that is sustained by a new extended linker ligand, [Cd(Imibz)2], X-dia-2-Cd, HImibz or 2 = 4-((4-(1H-imidazol-1-yl)phenylimino)methyl)benzoic acid. X-dia-2-Cd was found to exhibit reversible single-crystal-to-single-crystal (SC–SC) transformations between four distinct phases: an as-synthesised (from N,N-dimethylformamide) wide-pore phase, X-dia-2-Cd-α; a narrow-pore phase, X-dia-2-Cd-β, formed upon exposure to water; a narrow-pore phase obtained by activation, X-dia-2-Cd-γ; a medium-pore CO2-loaded phase X-dia-2-Cd-δ. While the space group remained constant in the four phases, the cell volumes and calculated void space ranged from 4988.7 Å3 and 47% (X-dia-2-Cd-α), respectively, to 3200.8 Å3 and 9.1% (X-dia-2-Cd-γ), respectively. X-dia-2-Cd-γ also exhibited a water vapour-induced structural transformation to the water-loaded X-dia-2-Cd-β phase, resulting in an S-shaped sorption isotherm. The inflection point occurred at 18% RH with negligible hysteresis on the desorption profile. Water vapour temperature-humidity swing cycling (60% RH, 300 K to 0% RH, 333 K) indicated hydrolytic stability of X-dia-2-Cd and working capacity was retained after 128 cycles of sorbent regeneration. CO2 (at 195 K) was also observed to induce a structural transformation in X-dia-2-Cd-γ and in situ PXRD studies at 1 bar of CO2, 195 K revealed the formation of X-dia-2-Cd-δ, which exhibited 31% larger unit cell volume than X-dia-2-Cd-γ.</p

Highly productive C3H4/C3H6 trace separation by a packing polymorph of a layered hybrid ultramicroporous material

Ultramicroporous materials can be highly effective at trace gas separations when they offer a high density of selective binding sites. Herein, we report that sql-NbOFFIVE-bpe-Cu, a new variant of a previously reported ultramicroporous square lattice, sql, topology material, sql-SIFSIX-bpe-Zn, can exist in two polymorphs. These polymorphs, sql-NbOFFIVE-bpe-Cu-AA (AA) and sql-NbOFFIVE-bpe-Cu-AB (AB), exhibit AAAA and ABAB packing of the sql layers, respectively. Whereas NbOFFIVE-bpe-Cu-AA (AA) is isostructural with sql?SIFSIX-bpe-Zn, each exhibiting intrinsic 1D channels, sql-NbOFFIVE-bpe-Cu-AB (AB) has two types of channels, the intrinsic channels and extrinsic channels between the sql networks. Gas and temperature induced transformations of the two polymorphs of sql-NbOFFIVE-bpe-Cu were investigated by pure gas sorption, single-crystal X-ray diffraction (SCXRD), variable temperature powder X-ray diffraction (VT-PXRD), and synchrotron PXRD. We observed that the extrinsic pore structure of AB resulted in properties with potential for selective C3H4/C3H6 separation. Subsequent dynamic gas breakthrough measurements revealed exceptional experimental C3H4/C3H6 selectivity (270) and a new benchmark for productivity (118 mmol g−1) of polymer grade C3H6 (purity >99.99%) from a 1:99 C3H4/C3H6 mixture. Structural analysis, gas sorption studies, and gas adsorption kinetics enabled us to determine that a binding “sweet spot” for C3H4 in the extrinsic pores is behind the benchmark separation performance. Density-functional theory (DFT) calculations and Canonical Monte Carlo (CMC) simulations provided further insight into the binding sites of C3H4 and C3H6 molecules within these two hybrid ultramicroporous materials, HUMs. These results highlight, to our knowledge for the first time, how pore engineering through the study of packing polymorphism in layered materials can dramatically change the separation performance of a physisorbent.</p