The development of new techniques and materials that can separate ethylene from ethane is highly relevant in modern applications. Although adsorption-based separation using metal–organic frameworks (MOFs) have gained increasing attention, the relatively low stability (especially water resistance) unscalable synthesis MOFs severely limit their application real industrial scenarios. Addressing these challenges, we rationally designed synthesized two C2H6-selective MOF adsorbents (NKMOF-8-Br...

Diverse crystal engineering principles employed in the discovery of porous coordination networks for selective separation C2 gases reveal that control pore size and chemistry emerges as key to unlock their outstanding performances.

Abstract 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 storage separation. Such behaviour is currently limited to a few dozen physisorbents typically switch through breathing mechanism requiring structural contortions. Here we show clathrate coordination network undergoes gas-induced multiple non-porous phases transient porosity, which involves the...

Ultramicroporous materials can be highly effective at trace gas separations when they offer a high density of selective binding sites. Herein, we report that

2D and 3D porous coordination networks (PCNs) as exemplified by metal–organic frameworks, MOFs, have garnered interest for their potential utility sorbents molecular separations storage. The inherent modularity of PCNs has enabled the development crystal engineering strategies systematic fine-tuning pore size chemistry in families related PCNs. same cannot be said about one-dimensional (1D) polymers, CPs, which are understudied with respect to porosity. Here, we report that permanent...

Abstract C3 hydrocarbons (HCs), especially propylene and propane, are high‐volume products of the chemical industry as they utilized for production fuels, polymers, commodities. Demand HCs building blocks is increasing but obtaining them in sufficient purity (>99.95%) polymer processes requires economically energetically costly methods such cryogenic distillation. Adsorptive separations using porous coordination networks (PCNs) could offer an energy‐efficient alternative to current...

Hybrid ultramicroporous materials, HUMs, are comprised of metal cations linked by combinations inorganic and organic ligands. Their modular nature makes them amenable to crystal engineering studies, which have thus far afforded four HUM platforms (as classified the linkers). HUMs practical interest because their benchmark gas separation performance for several industrial mixtures. We report herein design gram-scale synthesis prototypal sulfate-linked HUM, fsc topology coordination network...

Although pyrazine-linked hybrid ultramicroporous materials (HUMs, pore size <7 Å) are benchmark physisorbents for trace carbon dioxide (CO2 ) capture under dry conditions, their affinity water (H2 O) mitigates performance in humid conditions. Herein, we report on the co-adsorption of H2 O and CO2 by TIFSIX-3-Ni-a high HUM-and find that slow sorption kinetics can enable uptake release using shortened adsorption cycles with retention ca. 90 % uptake. Insight into is provided situ infrared...

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 switching mechanisms and pressures. In this work, we report two CNs, [Co(bimpy)(bdc)]n (X-dia-4-Co) [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), both...

Flexible metal–organic materials (FMOMs) with stepped isotherms can offer enhanced working capacity in storage applications such as adsorbed natural gas (ANG) storage. Unfortunately, whereas >1000 FMOMs are known, only a handful exhibit methane uptake of >150 cm3/cm3 at 65 atm and 298 K, conditions relevant to ANG. Here, we report double-walled 2-fold interpenetrated diamondoid (dia) network, X-dia-6-Ni, [Ni2L4(μ-H2O)]n, comprising new azo linker ligand, L– (L– =...

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: as-synthesised (from N,N-dimethylformamide)...

High and increasing production of separation C8 aromatic isomers demands the development purification methods that are efficient, scalable, inexpensive, especially for p-xylene, PX, largest volume commodity. Herein, we report 4-(1H-1,2,4-triazol-1-yl)-phenyl-1H-benzo[de]isoquinoline-1,3(2H)-dione (TPBD), a molecular compound can be prepared scaled up via solid-state synthesis, exhibits exceptional PX selectivity over each other isomers, o-xylene (OX), m-xylene (MX), ethylbenzene (EB). The...

Herein, we report the crystal structure and guest binding properties of a new two-dimensional (2D) square lattice (sql) topology coordination network, sql-(azpy)(pdia)-Ni, which is comprised two linker ligands with diazene (azo) moieties, (E)-1,2-di(pyridin-4-yl)diazene(azpy) (E)-5-(phenyldiazenyl)isophthallate(pdia). sql-(azpy)(pdia)-Ni underwent guest-induced switching between closed (nonporous) β phase several open (porous) α phases, but unlike clay-like layer expansion to distinct phases...

Propane (C3H8) is a widely used fuel gas. Metal–organic framework (MOF) physisorbents that are C3H8 selective offer the potential to significantly reduce energy footprint for capturing from natural gas, where typically present as minor component. Here we report recovery performance of previously unreported lonsdaleite, lon, topology MOF, chiral metal–organic material, [Ni(S-IEDC)(bipy)(SCN)]n, CMOM-7. CMOM-7 was prepared three low-cost precursors: Ni(SCN)2, S-indoline-2-carboxylic acid...

Hybrid ultramicroporous materials (HUMs), metal-organic platforms that incorporate inorganic pillars, are a promising class of porous solids. A key area interest for such is gas separation, where HUMs have already established benchmark performances. Thanks to their ready compositional modularity, we report the design and synthesis new HUM, GEFSIX-21-Cu, incorporating ligand pypz (4-(3,5-dimethyl-1H-pyrazol-4-yl)pyridine, 21) GeF62- pillaring anions. GEFSIX-21-Cu delivers on two fronts:...

We report a water induced phase transformation in flexible MOF, [Zn3(OH)2(btca)2] (Hbtca = 1H-benzotriazole-5-carboxylic acid), that exhibits two-step vapor sorption isotherm associated with water-induced transformations. Variable temperature X-ray diffraction studies revealed the dehydrated phase, LP-β, is almost isostructural previously reported solvated LP-α. LP-β reversibly transformed to partially hydrated NP, at 5% RH, and fully LP-γ, 47% RH. Structural reveal host–guest guest–guest...

Guest transport through discrete voids (closed pores) in crystalline solids is poorly understood. Herein, we report the gas sorption properties of a nonporous coordination network, [Co(bib)2Cl2]n·2MeOH (sql‐bib‐Co‐Cl‐α), featuring square lattice (sql) topology and bent linker 1,3‐bis(1H‐imidazol‐1‐yl)benzene (bib). The as‐synthesized sql‐bib‐Co‐Cl‐α has 11.3% (313 Å3) its unit cell volume closed pores occupied by methanol (MeOH). Upon desolvation air exposure, underwent single‐crystal to...

Guest transport through discrete voids (closed pores) in crystalline solids is poorly understood. Herein, we report the gas sorption properties of a nonporous coordination network, [Co(bib)2Cl2]n·2MeOH (sql‐bib‐Co‐Cl‐α), featuring square lattice (sql) topology and bent linker 1,3‐bis(1H‐imidazol‐1‐yl)benzene (bib). The as‐synthesized sql‐bib‐Co‐Cl‐α has 11.3% (313 Å3) its unit cell volume closed pores occupied by methanol (MeOH). Upon desolvation air exposure, underwent single‐crystal to...

An emerging strategy in the design of efficient gas storage technologies is development stimuli-responsive physisorbents which undergo transformations 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...

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 control gas sorption properties for CO2 C3 Specifically, bimbz (1,4-bis(imidazol-1-yl)benzene) in coordination network X-ddi-1-Ni ([Ni2(bimbz)2(bdc)2(H2O)]n, H2bdc = 1,4-benzenedicarboxylic...

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 are best exemplified electron-rich fluorinated anions, e.g., SiF62–, TiF62–, and NbOF52–, although sulfate have recently been highlighted inexpensive earth-friendly alternatives. Herein, we report the use of a rare copper dimer molecular building block to generate two square lattice, sql, which be prepared via solvent...

The stimulus-responsive behavior of coordination networks (CNs), which switch between closed (nonporous) and open (porous) phases, is interest because its potential utility in gas storage separation. Herein, we report two polymorphs a new square-lattice (sql) topology CN, X-sql-1-Cu, formula [Cu(Imibz)2]n (HImibz = {[4-(1H-imidazol-1-yl)phenylimino]methyl}benzoic acid), isolated from the as-synthesized CN X-sql-1-Cu-(MeOH)2·2MeOH, subsequently transformed to narrow pore solvate,...

We report a crystal-engineering study conducted upon platform of three mixed-linker square lattice (sql) coordination networks general formula [Zn(Ria)(bphy)] [bphy = 1,2-bis(pyridin-4-yl)hydrazine, H2Ria 5-position-substituted isophthalic acid, and R -Br, -NO2, -OH; compounds 1-3]. Analysis single-crystal X-ray diffraction data 1-2 the simulated crystal structure 3 revealed that 1-3 are isomorphous sustained by bilayers sql linked hydrogen bonds. Although similar pore shapes sizes exist in...

This study explores the use of diamine chelating ligands in two prototypal hybrid ultramicroporous materials for acetylene-selective separation from carbon dioxide. One, SOFOUR-2-Zn, uses eco-friendly sulphate anion as a pillar.