Dinuclear Copper Sulfate-Based Square Lattice Topology Network with High Alkyne Selectivity.

Porous coordination networks (PCNs) sustained by inorganic anions that serve as linker ligands can offer high selectivity toward specific gases or vapors in gas mixtures. Such inorganic anions are best exemplified by electron-rich fluorinated anions, e.g., SiF62-, TiF62-, and NbOF52-, although sulfate anions have recently been highlighted as inexpensive and earth-friendly alternatives. Herein, we report the use of a rare copper sulfate dimer molecular building block to generate two square lattice, sql, coordination networks which can be prepared via solvent layering or slurrying, CuSO4(1,4-bib)1.5, 1, (1,4-bib = 1,4-bisimidazole benzene) and CuSO4(1,4-bin)1.5, 2, (1,4-bin = 1,4-bisimidazole naphthalene). Variable-temperature SCXRD and PXRD experiments revealed that both sql networks underwent reversible structural transformations due to linker rotations or internetwork displacements. Gas sorption studies conducted upon the narrow-pore phase of CuSO4(1,4-bin)1.5, 2np, found a high calculated 1:99 selectivity for C2H2 over C2H4 (33.01) and CO2 (15.18), as well as strong breakthrough performance. Across-the-board, C3H4 selectivity vs C3H6, CO2, and C3H8 was also observed. Sulfate-based PCNs, although still understudied, appear increasingly likely to offer utility in gas and vapor separations.

Metal cation substitution can tune CO2, H2O and CH4 switching pressure in transiently porous coordination networks.

Compared to rigid physisorbents, switching coordination networks that reversibly transform between closed (non-porous) and open (porous) phases offer promise for gas/vapour storage and separation owing to their improved working capacity and desirable thermal management properties. We recently introduced a coordination network, X-dmp-1-Co, which exhibits switching enabled by transient porosity. The resulting "open" phases are generated at threshold pressures even though they are conventionally non-porous. Herein, we report that X-dmp-1-Co is the parent member of a family of transiently porous coordination networks [X-dmp-1-M] (M = Co, Zn and Cd) and that each exhibits transient porosity but switching events occur at different threshold pressures for CO2 (0.8, 2.1 and 15 mbar, for Co, Zn and Cd, respectively, at 195 K), H2O (10, 70 and 75% RH, for Co, Zn and Cd, respectively, at 300 K) and CH4 (<2, 10 and 25 bar, for Co, Zn and Cd, respectively, at 298 K). Insight into the phase changes is provided through in situ SCXRD and in situ PXRD. We attribute the tuning of gate-opening pressure to differences and changes in the metal coordination spheres and how they impact dpt ligand rotation. X-dmp-1-Zn and X-dmp-1-Cd join a small number of coordination networks (<10) that exhibit reversible switching for CH4 between 5 and 35 bar, a key requirement for adsorbed natural gas storage.

Water vapour induced structural flexibility in a square lattice coordination network.

Herein, we introduce a new square lattice topology coordination network, sql-(1,3-bib)(ndc)-Ni, with three types of connection and detail its gas and vapour induced phase transformations. Exposure to humidity resulted in an S-shaped isotherm profile, suggesting potential utility of such materials as desiccants.

Control over Phase Transformations in a Family of Flexible Double Diamondoid Coordination Networks through Linker Ligand Substitution.

In this work, we present the first metal-organic framework (MOF) platform with a self-penetrated double diamondoid (ddi) topology that exhibits switching between closed (nonporous) and open (porous) phases induced by exposure to gases. A crystal engineering strategy, linker ligand substitution, was used to control gas sorption properties for CO2 and C3 gases. Specifically, bimbz (1,4-bis(imidazol-1-yl)benzene) in the coordination network X-ddi-1-Ni ([Ni2(bimbz)2(bdc)2(H2O)]n, H2bdc = 1,4-benzenedicarboxylic acid) was replaced by bimpz (3,6-bis(imidazol-1-yl)pyridazine) in X-ddi-2-Ni ([Ni2(bimpz)2(bdc)2(H2O)]n). In addition, the 1:1 mixed crystal X-ddi-1,2-Ni ([Ni2(bimbz)(bimpz)(bdc)2(H2O)]n) was prepared and studied. All three variants form isostructural closed (ß) phases upon activation which each exhibited different reversible properties upon exposure to CO2 at 195 K and C3 gases at 273 K. For CO2, X-ddi-1-Ni revealed incomplete gate-opening, X-ddi-2-Ni exhibited a stepped isotherm with saturation uptake of 3.92 mol·mol-1, and X-ddi-1,2-Ni achieved up to 62% more gas uptake and a distinct isotherm shape vs the parent materials. Single-crystal X-ray diffraction (SCXRD) and in situ powder X-ray diffraction (PXRD) experiments provided insight into the mechanisms of phase transformation and revealed that the ß phases are nonporous with unit cell volumes 39.9, 40.8, and 41.0% lower than the corresponding as-synthesized α phases, X-ddi-1-Ni-α, X-ddi-2-Ni-α, and X-ddi-1,2-Ni-α, respectively. The results presented herein represent the first report of reversible switching between closed and open phases in ddi topology coordination networks and further highlight how ligand substitution can profoundly impact the gas sorption properties of switching sorbents.

One Atom Can Make All the Difference: Gas-Induced Phase Transformations in Bisimidazole-Linked Diamondoid Coordination Networks.

Coordination networks (CNs) that undergo gas-induced transformation from closed (nonporous) to open (porous) structures are of potential utility in gas storage applications, but their development is hindered by limited control over their switching mechanisms and pressures. In this work, we report two CNs, [Co(bimpy)(bdc)]n (X-dia-4-Co) and [Co(bimbz)(bdc)]n (X-dia-5-Co) (H2bdc = 1,4-benzendicarboxylic acid; bimpy = 2,5-bis(1H-imidazole-1-yl)pyridine; bimbz = 1,4-bis(1H-imidazole-1-yl)benzene), that both undergo transformation from closed to isostructural open phases involving at least a 27% increase in cell volume. Although X-dia-4-Co and X-dia-5-Co only differ from one another by one atom in their N-donor linkers (bimpy = pyridine, and bimbz = benzene), this results in different pore chemistry and switching mechanisms. Specifically, X-dia-4-Co exhibited a gradual phase transformation with a steady increase in the uptake when exposed to CO2, whereas X-dia-5-Co exhibited a sharp step (type F-IV isotherm) at P/P0 ≈ 0.008 or P ≈ 3 bar (195 or 298 K, respectively). Single-crystal X-ray diffraction, in situ powder XRD, in situ IR, and modeling (density functional theory calculations, and canonical Monte Carlo simulations) studies provide insights into the nature of the switching mechanisms and enable attribution of pronounced differences in sorption properties to the changed pore chemistry.

Crystal Engineering of Two Light and Pressure Responsive Physisorbents.

An emerging strategy in the design of efficient gas storage technologies is the development of stimuli-responsive physisorbents which undergo transformations in response to a particular stimulus, such as pressure, heat or light. Herein, we report two isostructural light modulated adsorbents (LMAs) containing bis-3-thienylcyclopentene (BTCP), LMA-1 [Cd(BTCP)(DPT)2 ] (DPT=2,5-diphenylbenzene-1,4-dicarboxylate) and LMA-2 [Cd(BTCP)(FDPT)2 ] (FDPT=5-fluoro-2,diphenylbenzene-1,4-dicarboxylate). Both LMAs undergo pressure induced switching transformations from non-porous to porous via adsorption of N2 , CO2 and C2 H2 . LMA-1 exhibited multi-step adsorption while LMA-2 showed a single-step adsorption isotherm. The light responsive nature of the BTPC ligand in both frameworks was exploited with irradiation of LMA-1 resulting in a 55 % maximum reduction of CO2 uptake at 298 K. This study reports the first example of a switching sorbent (closed to open) that can be further modulated by light.

Reversible transformations between the non-porous phases of a flexible coordination network enabled by transient porosity.

Flexible metal-organic materials that exhibit stimulus-responsive switching between closed (non-porous) and open (porous) structures induced by gas molecules are of potential utility in gas storage and separation. Such behaviour is currently limited to a few dozen physisorbents that typically switch through a breathing mechanism requiring structural contortions. Here we show a clathrate (non-porous) coordination network that undergoes gas-induced switching between multiple non-porous phases through transient porosity, which involves the diffusion of guests between discrete voids through intra-network distortions. This material is synthesized as a clathrate phase with solvent-filled cavities; evacuation affords a single-crystal to single-crystal transformation to a phase with smaller cavities. At 298 K, carbon dioxide, acetylene, ethylene and ethane induce reversible switching between guest-free and gas-loaded clathrate phases. For carbon dioxide and acetylene at cryogenic temperatures, phases showing progressively higher loadings were observed and characterized using in situ X-ray diffraction, and the mechanism of diffusion was computationally elucidated.

Large negative linear compressibility of a porous molecular co-crystal.

Flexible and transformable molecules, particularly those responding to external stimuli, are needed for designing sensors and porous compounds capable of storing or separating gases and liquids. Under normal conditions the photochromic compound, 1,2-bis[2-methyl-5-(pyridyl)-3thienyl]cyclopentene (BTCP) forms a porous co-crystal with 1,4-diiodotetrafluorobenzene (dItFB). It traps acetone (Ac) molecules in the pores. Owing to a unique system of pores in the polar framework, the crystal is sensitive to the humidity in the air and to the chosen liquid environment. When compressed in non-penetrating media, the crystal displays a strong negative linear compressibility (NLC) along [100].

Guest-Induced Structural Transformations in a Porous Halogen-Bonded Framework.

Structural evidence obtained from in situ X-ray diffraction shows that halogen bonding is responsible for the formation of a dynamic porous molecular solid. This material is surprisingly robust and undergoes reversible switching of its pore volume by activation or by exposure to a series of gases of different sizes and shapes. Volumetric gas sorption and pressure-gradient differential scanning calorimetry (P-DSC) data provide further mechanistic insight into the breathing behavior.

Correction: Inherently chiral calix[4]arenes via oxazoline directed ortholithiation: synthesis and probe of chiral space.

[This corrects the article DOI: 10.3762/bjoc.10.291.].

Inherently chiral calix[4]arenes via oxazoline directed ortholithiation: synthesis and probe of chiral space.

The diastereoselective oxazoline-directed lithiation of calix[4]arenes is reported with diastereoselective ratios of greater than 100:1 in some instances. Notably, it has been found that the opposite diastereomer can be accessed via this approach merely through the choice of an alkyllithium reagent. The inherently chiral oxazoline calix[4]arenes have also been preliminarily examined as ligands in the palladium-catalyzed Tsuji-Trost allylation reaction, returning results comparable to their planar chiral ferrocene counterparts pointing towards future application of these types of compounds.

Manipulating the diastereoselectivity of ortholithiation in planar chiral ferrocenes.

The sense of asymmetric ortholithiation directed by a chiral oxazoline may be inverted simply by the choice of achiral ligand. Comparison of results with a number of ferrocenyl oxazoline derivatives suggests that lithiation takes place by coordination to the oxazoline nitrogen irrespective of the ligand used.