Hydrogen-bonded organic frameworks for membrane separation.

Hydrogen-bonded organic frameworks (HOFs) are a new class of crystalline porous materials that are formed through the interconnection of organic or metal-organic building units via intermolecular hydrogen bonds. The remarkable flexibility and reversibility of hydrogen bonds, coupled with the customizable nature of organic units, endow HOFs with mild synthesis conditions, high crystallinity, solvent processability, and facile self-healing and regeneration properties. Consequently, these features have garnered significant attention across various fields, particularly in the realm of membrane separation. Herein, we present an overview of the recent advances in HOF-based membranes, including their advanced fabrication strategies and fascinating applications in membrane separation. To attain the desired HOF-based membranes, careful consideration is dedicated to crucial factors such as pore size, stability, hydrophilicity/hydrophobicity, and surface charge of the HOFs. Additionally, diverse preparation methods for HOF-based membranes, including blending, in situ growth, solution-processing, and electrophoretic deposition, have been analyzed. Furthermore, applications of HOF-based membranes in gas separation, water treatment, fuel cells, and other emerging application areas are presented. Finally, the challenges and prospects of HOF-based membranes are critically pointed out.

Self-Healing Hydrogen-Bonded Organic Frameworks for Low-Concentration Ammonia Capture.

The self-healing behavior has been extensively used in intelligent sensing systems capable of molecular recognition. However, most rigid crystalline frameworks, once collapsed under external stimuli like pressure, heat, or vacuum, could hardly recover to their crystalline phases under ambient conditions. Here, we report the self-healing of a new microporous hydrogen-bonded organic framework, FDU-HOF-3 (FDU = Fudan University), for ammonia (NH3) capture and compared it with the established mesoporous HOF-101. With the introduction of low-concentration NH3 into the pores, the HOFs became disordered but were then simply heated under a vacuum to return to their original crystalline states after NH3 removal. Close characterizations revealed that the repeatable self-healing behavior of these HOFs was achieved due to the COOH-NH3 acid-base interactions accompanied by the breaking and regeneration of complementary COOH-COOH hydrogen bonds. FDU-HOF-3 showed a record-capturing capability for low-concentration NH3 (8.13 mmol/g at 25 mbar) among all HOFs and displayed a quick photocurrent decrease after exposure to 250 ppm NH3 for less than 10 s. These self-healing HOFs were used to capture and release NH3 for over 10 cycles without any decrease in the adsorption capacities.

Metal-Organic Framework with Space-Partition Pores by Fluorinated Anions for Benchmark C2H2/CO2 Separation.

The efficient separation of C2H2 from C2H2/CO2 or C2H2/CO2/CH4 mixtures is crucial for achieving high-purity C2H2 (>99%), essential in producing contemporary commodity chemicals. In this report, we present ZNU-12, a metal-organic framework with space-partitioned pores formed by inorganic fluorinated anions, for highly efficient C2H2/CO2 and C2H2/CO2/CH4 separation. The framework, partitioned by fluorinated SiF62- anions into three distinct cages, enables both a high C2H2 capacity (176.5 cm3/g at 298 K and 1.0 bar) and outstanding C2H2 selectivity over CO2 (13.4) and CH4 (233.5) simultaneously. Notably, we achieve a record-high C2H2 productivity (132.7, 105.9, 98.8, and 80.0 L/kg with 99.5% purity) from C2H2/CO2 (v/v = 50/50) and C2H2/CO2/CH4 (v/v = 1/1/1, 1/1/2, or 1/1/8) mixtures through a cycle of adsorption-desorption breakthrough experiments with high recovery rates. Theoretical calculations suggest the presence of potent "2 + 2" collaborative hydrogen bonds between C2H2 and two hexafluorosilicate (SiF62-) anions in the confined cavities.

Self-Healing B ← N-Based Hydrogen-Bonded Organic Framework for Exclusive Recognition and Separation of Toluene from Methyl-Cyclohexane.

The effective separation of aromatic and aliphatic hydrocarbons remains a notable challenge in the petrochemical industry. Herein, we report a self-healing three-dimensional B ← N-based hydrogen-bonded organic framework (HOF), BN-HOF-1, constructed from discrete B ← N inclusive dimers through weak C-H···F and C-H···N hydrogen-bonding interactions. To make use of the specific recognition of the B ← N inclusive dimers for the toluene molecules and the reversible ad/desorption nature of this novel HOF, BN-HOF-1 can exclusively recognize and separate toluene from the mixtures of toluene-methylcyclohexane, thus generating 99.6% pure toluene from its mixtures after gentle heating, the recorded value among any reported materials for toluene purification. After the toluene molecules were released from the framework, it becomes the condensed BN-HOF-1a, which can be further reused for the highly selective recognition and purification of toluene from its binary mixtures, through the reversible structural recovery back to BN-HOF-1. Single-crystal X-ray diffraction and molecular modeling studies reveal that the high specific toluene recognition is attributed to the complementary electrostatic potential between the host B ← N inclusive dimers and the guest toluene, while the self-healing and recovery nature of this HOF is attributed to weak intermolecular hydrogen-bonding interactions.

Orthogonal Postsynthetic Copolymerization of Hydrogen-Bonded Organic Frameworks into a PolyHOF Membrane.

Hydrogen-bonded organic frameworks (HOFs) have shown promise in various fields; however, the construction of HOF/polymer hybrid membranes that can maintain both structural and functional integrity remains challenging. In this study, we here fabricated a new HOF (HOF-50) with reserved polymerizable allyl group via charge-assisted H-bonds between the carboxylate anion and amidinium, and subsequently copolymerized the HOF with monomers to construct a covalently bonded HOF/polymer hybrid (polyHOF) membrane. The resulting polyHOF membrane not only exhibits customizable mechanical properties and extreme stability, but also shows an exceptional ratiometric luminescent temperature-sensing function with very high sensitivity and visibility even when the lanthanide content is two orders of magnitude lower than that of the reported mixed-lanthanide metal-organic frameworks (MOFs) and lanthanide-doped covalent organic frameworks (COFs). This orthogonal postsynthesis copolymerization strategy may provide a general approach for preparing covalently connected HOF/polymer hybrid membranes for diverse applications.

Anionic Hydrogen-Bonded Frameworks Showing Tautomerism and Colorful Luminescence for the Ultrasensitive Detection of Acetone.

Tautomers coexisting in an equilibrium system have significant potential for regulating luminescent properties because of their structural differences. However, separating and stabilizing tautomers at room temperature is a considerable challenge. In this study, it is found that hydrogen-bonded organic frameworks (HOFs) composed of Br- anions can effectively separate and stabilize two proton-transfer tautomers of triarylformamidinium bromide: namely, the nitrogen cation (BA-N) and carbon cation (BA-C). The BA-N crystal consisting of a dense anionic HOF and parallelly aligned organic cations exhibits green thermally activated delayed fluorescence and red room-temperature phosphorescence (RTP). The BA-C crystal contains acetone molecules that induce an antiparallel arrangement of the organic cations to form a loose HOF, producing blue prompt fluorescence and green RTP. Interestingly, switching of the HOFs between BA-N and BA-C can be achieved through the uptake and release of acetone, thereby dynamically adjusting multiple luminescent properties. Consequently, the HOF crystals can be used for the highly sensitive and specific sensing of acetone with a detection limit of 66.74 ppm. This study not only stabilizes tautomeric luminescent materials at room temperature, but also provides a new method for constructing smart HOFs with a sensitive response to a stimulus.

Supramolecular Entanglement in a Hydrogen-Bonded Organic Framework Enables Flexible-Robust Porosity for Highly Efficient Purification of Natural Gas.

The development of porous materials with flexible-robust characteristics shows some unique advantages to target high performance for gas separation, but remains a daunting challenge to achieve so far. Herein, we report a carboxyl-based hydrogen-bonded organic framework (ZJU-HOF-8a) with flexible-robust porosity for efficient purification of natural gas. ZJU-HOF-8a features a four-fold interpenetrated structure with dia topology, wherein abundant supramolecular entanglements are formed between the adjacent subnetworks through weak intermolecular hydrogen bonds. This structural configuration could not only stabilize the whole framework to establish the permanent porosity, but also enable the framework to show some flexibility due to its weak intermolecular interactions (so-called flexible-robust framework). The flexible-robust porosity of ZJU-HOF-8a was exclusively confirmed by gas sorption isotherms and single-crystal X-ray diffraction studies, showing that the flexible pore pockets can be opened by C3H8 and n-C4H10 molecules rather by C2H6 and CH4. This leads to notably higher C3H8 and n-C4H10 uptakes with enhanced selectivities than C2H6 over CH4 under ambient conditions, affording one of the highest n-C4H10/CH4 selectivities. The gas-loaded single-crystal structures coupled with theoretical simulations reveal that the loading of n-C4H10 can induce an obvious framework expansion along with pore pocket opening to improve n-C4H10 uptake and selectivity, while not for C2H6 adsorption. This work suggests an effective strategy of designing flexible-robust HOFs for improving gas separation properties.

Reverse Separation of Carbon Dioxide and Acetylene in Two Isostructural Copper Pyridine-Carboxylate Frameworks.

Separating acetylene from carbon dioxide is important but highly challenging due to their similar molecular shapes and physical properties. Adsorptive separation of carbon dioxide from acetylene can directly produce pure acetylene but is hardly realized because of relatively polarizable acetylene binds more strongly. Here, we reverse the CO2 and C2H2 separation by adjusting the pore structures in two isoreticular ultramicroporous metal-organic frameworks (MOFs). Under ambient conditions, copper isonicotinate (Cu(ina)2), with relatively large pore channels shows C2H2-selective adsorption with a C2H2/CO2 selectivity of 3.4, whereas its smaller-pore analogue, copper quinoline-5-carboxylate (Cu(Qc)2) shows an inverse CO2/C2H2 selectivity of 5.6. Cu(Qc)2 shows compact pore space that well matches the optimal orientation of CO2 but is not compatible for C2H2. Neutron powder diffraction experiments confirmed that CO2 molecules adopt preferential orientation along the pore channels during adsorption binding, whereas C2H2 molecules bind in an opposite fashion with distorted configurations due to their opposite quadrupole moments. Dynamic breakthrough experiments have validated the separation performance of Cu(Qc)2 for CO2/C2H2 separation.

Optimal Binding Affinity for Sieving Separation of Propylene from Propane in an Oxyfluoride Anion-Based Metal-Organic Framework.

Highly efficient adsorptive separation of propylene from propane offers an ideal alternative method to replace the energy-intensive cryogenic distillation technology. Molecular sieving-type separation via high-performance adsorbents is targeted for superior selectivity, but the limit in adsorption capacity remains a great challenge. Here, we report an oxyfluoride-based ultramicroporous metal-organic framework UTSA-400, [Ni(WO2F4)(pyz)2] (pyz = pyrazine), featuring one-dimensional pore channels that can accommodate the propylene molecules with optimal binding affinity while specifically excluding the propane molecules. The exposed oxide/fluoride pairs in UTSA-400 serve as strong functional sites for strengthened propylene-host interactions, accounting for a significantly enhanced propylene uptake, while the propane molecules are excluded due to the regulated host framework dynamics. The strong propylene binding enables near-saturation of propylene in the pore confinement at ambient conditions, leading to full utilization of pore space and superior packing density. Combined in situ infrared spectroscopy measurements and dispersion-corrected density functional theory calculations clearly unveil the nature of boosted host-guest binding. Direct production of polymer-grade (>99.5%) propylene with remarkable dynamic productivity is demonstrated by column breakthrough experiments. This work presents an example of pore engineering with atomic precision to break the trade-off in adsorptive separation through guest binding optimization.

Programmed Polarizability Engineering in a Cyclen-Based Cubic Zr(IV) Metal-Organic Framework to Boost Xe/Kr Separation.

Efficient separation of xenon (Xe) and krypton (Kr) mixtures through vacuum swing adsorption (VSA) is considered the most attractive route to reduce energy consumption, but discriminating between these two gases is difficult due to their similar properties. In this work, we report a cubic zirconium-based MOF (Zr-MOF) platform, denoted as NU-1107, capable of achieving selective separation of Xe/Kr by post-synthetically engineering framework polarizability in a programmable manner. Specifically, the tetratopic linkers in NU-1107 feature tetradentate cyclen cores that are capable of chelating a variety of transition-metal ions, affording a sequence of metal-docked cationic isostructural Zr-MOFs. NU-1107-Ag(I), which features the strongest framework polarizability among this series, achieves the best performance for a 20:80 v/v Xe/Kr mixture at 298 K and 1.0 bar with an ideal adsorbed solution theory (IAST) predicted selectivity of 13.4, placing it among the highest performing MOF materials reported to date. Notably, the Xe/Kr separation performance for NU-1107-Ag(I) is significantly better than that of the isoreticular, porphyrin-based MOF-525-Ag(II), highlighting how the cyclen core can generate relatively stronger framework polarizability through the formation of low-valent Ag(I) species and polarizable counteranions. Density functional theory (DFT) calculations corroborate these experimental results and suggest strong interactions between Xe and exposed Ag(I) sites in NU-1107-Ag(I). Finally, we validated this framework polarizability regulation approach by demonstrating the effectiveness of NU-1107-Ag(I) toward C3H6/C3H8 separation, indicating that this generalizable strategy can facilitate the bespoke synthesis of polarized porous materials for targeted separations.

Remarkably Selective Propylene-Propane Separation Using a Copper Scorpionate.

Propylene is a crucial building block to produce many industrial-scale chemicals including polypropylene. The separation of propylene from propane to reach the high-purity levels needed for downstream applications is a difficult task due to the close similarities in their physical properties. The olefin/paraffin separation including that involving propylene mainly relies on highly energy-intensive distillation processes and accounts for nearly 0.3% of the global energy consumption. The utility of a copper complex supported by a fluorinated bis(pyrazolyl)borate is demonstrated to accomplish the separation of propylene from propane repeatedly, under mild conditions with high selectivity. Complete characterization of a rare, copper(I) propylene complex is also reported including the molecular structure.

Exploring Multifunctional Hydrogen-Bonded Organic Framework Materials.

Hydrogen-bonded organic framework (HOF) materials have provided a new dimension and bright promise as a new platform for developing multifunctional materials. They can be readily self-assembled from their corresponding organic molecules with diverse functional sites such as carboxylic acid and amine groups for their hydrogen bonding and aromatic ones for their weak π···π interactions to stabilize the frameworks. Compared with those established porous materials such as zeolites, metal-organic frameworks (MOFs), and covalent-organic frameworks (COFs), it is much more difficult to stabilize HOFs and thus establish their permanent porosities given the fact that hydrogen bonds are typically weaker than ionic, coordination, and covalent bonds. But it provides the uniqueness of HOF materials in which they can be easily recovered and regenerated through simple recrystallization. HOF materials can also be easily and straightforwardly processed and very compatible with the biomolecules, making them potentially very useful materials for industrial and biomedical applications. The reversible and weak bonding nature of the hydrogen bonds can be readily utilized to construct flexible porous HOF materials in which we can tune the temperature and pressure to control their porosities and, thus, their diverse applications, for example, on gas separations, gas storage, drug delivery, and sensing. Some specific organic functional groups are quite directional for the hydrogen bond formations; for example, carboxylic acid prefers to form a directional dimer, which has enabled us to readily construct reticular porous HOF materials whose pores can be systematically tuned. In this Account, we outline our journey of exploring this new type of porous material by establishing one of the first porous HOFs in 2011 and thus developing its diverse applications. We have been able to use organic molecules with different functional sites, including 2,4-diaminotriazine (DAT), carboxylic acid (COOH), aldehyde (CHO), and cyano (CN), to construct porous HOFs. Through tuning the pore sizes, introducing specific binding sites, and making use of the framework flexibility, we have realized a series of HOF materials for the gas separations of C2H2/C2H4, C2H4/C2H6, C3H6/C3H8, C2H2/CO2, CO2/N2, and Xe/Kr and enantioselective separation of alcohols. To make use of optically active organic molecules, we have developed HOF materials for their luminescent sensing and optical lasing. Our research endeavors on multifunctional HOF materials have initiated extensive research in this emerging research topic among chemistry and materials sciences communities. We foresee that not only many more HOF materials will be developed but novel functions will be fulfilled beyond our imaginations soon.

Dual-Emitting Mixed-Lanthanide Metal-Organic Framework for Ratiometric and Quantitative Visual Detection of 2,6-Pyridine Dicarboxylic Acid.

The detection of the major biomarker of Bacillus anthracis, 2,6-dipicolinic acid (DPA), has attracted great interest in recent years. In this work, mixed-lanthanide metal-organic frameworks (M'LnMOFs), TbxEu1-x-cppa (cppa = 5-(5-carboxypyridin-3-yl)isophthalic acid), with different Tb/Eu ratios, were solvothermally synthesized. The results reveal that ratiometric fluorescent probe [Tb0.533Eu0.467-(Hcppa)1.5(H2O)(DMF)]·3H2O is water and acid-base stable and exhibits excellent sensitivity (LOD = 2.286 µM), high selectivity, and fast response (<2 min) for the detection of DPA. Due to the blocked energy transfer from Tb3+ to Eu3+ and the inner filter effect upon the addition of DPA, the fluorescent probe shows a distinct color change from orange-red to green. Furthermore, the visual detection of DPA was realized by identifying the RGB values of MOF-based agarose hydrogel films via a smartphone, highlighting the practical application of the fluorescent probe for DPA detection under aqueous solution conditions.

A Multimodal Ratiometric Luminescent Thermometer Based on a Single-Dysprosium Metal-Organic Framework.

The design of high-performance luminescent MOF thermometers with multi-operation modes has been long sought but remains a formidable challenge. In this work, for the first time, we present a multimodal luminescent ratiometric thermometer based on the single-lanthanide metal-organic framework (MOF) DyTPTC-2Me (H4TPTC-2Me = 2',5'-dimethyl-[1,1':4',1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid). It not only has the characteristic luminescence of Dy3+ in which the atomic transitions from the 4I15/2 and 4F9/2 states (thermally coupled energy levels, TCELs) are included but also emits ligand fluorescence due to the efficient energy back-transfer of Dy3+ to the ligand, thus allowing accurate non-invasive determination of temperature by different modes. In particular, the TCEL-based emissions of the Dy3+ ions give ideal signals for measuring the temperature in the 303-423 K range. The emissions of the ligand and Dy3+ (4F9/2 → 6H13/2) are used for temperature sensing in the range of 423 to 503 K. Both two modes feature promising thermometric performance, including high relative sensitivity, high temperature resolution, and excellent repeatability. Their combination is thus beneficial to achieve more accurate temperature detection over a broad temperature range, which can broaden the application scope of the ratiometric luminescent thermometers.

Fluorinated metal-organic frameworks for gas separation.

Fluorinated metal-organic frameworks (F-MOFs) as fast-growing porous materials have revolutionized the field of gas separation due to their tunable pore apertures, appealing chemical features, and excellent stability. A deep understanding of their structure-performance relationships is critical for the synthesis and development of new F-MOFs. This critical review has focused on several strategies for the precise design and synthesis of new F-MOFs with structures tuned for specific gas separation purposes. First, the basic principles and concepts of F-MOFs as well as their structure, synthesis and modification and their structure to property relationships are studied. Then, applications of F-MOFs in adsorption and membrane gas separation are discussed. A detailed account of the design and capabilities of F-MOFs for the adsorption of various gases and the governing principles is provided. In addition, the exceptional characteristics of highly stable F-MOFs with engineered pore size and tuned structures are put into perspective to fabricate selective membranes for gas separation. Systematic analysis of the position of F-MOFs in gas separation revealed that F-MOFs are benchmark materials in most of the challenging gas separations. The outlook and future directions of the science and engineering of F-MOFs and their challenges are highlighted to tackle the issues of overcoming the trade-off between capacity/permeability and selectivity for a serious move towards industrialization.

Topological Design of Unprecedented Metal-Organic Frameworks Featuring Multiple Anion Functionalities and Hierarchical Porosity for Benchmark Acetylene Separation.

Separation of acetylene (C2 H2 ) from carbon dioxide (CO2 ) or ethylene (C2 H4 ) is industrially important but still challenging so far. Herein, we developed two novel robust metal organic frameworks AlFSIX-Cu-TPBDA (ZNU-8) with znv topology and SIFSIX-Cu-TPBDA (ZNU-9) with wly topology for efficient capture of C2 H2 from CO2 and C2 H4 . Both ZNU-8 and ZNU-9 feature multiple anion functionalities and hierarchical porosity. Notably, ZNU-9 with more anionic binding sites and three distinct cages displays both an extremely large C2 H2 capacity (7.94 mmol/g) and a high C2 H2 /CO2 (10.3) or C2 H2 /C2 H4 (11.6) selectivity. The calculated capacity of C2 H2 per anion (4.94 mol/mol at 1 bar) is the highest among all the anion pillared metal organic frameworks. Theoretical calculation indicated that the strong cooperative hydrogen bonds exist between acetylene and the pillared SiF6 2- anions in the confined cavity, which is further confirmed by in situ IR spectra. The practical separation performance was explicitly demonstrated by dynamic breakthrough experiments with equimolar C2 H2 /CO2 mixtures and 1/99 C2 H2 /C2 H4 mixtures under various conditions with excellent recyclability and benchmark productivity of pure C2 H2 (5.13 mmol/g) or C2 H4 (48.57 mmol/g).

A Microporous Hydrogen-Bonded Organic Framework Based on Hydrogen-Bonding Tetramers for Efficient Xe/Kr Separation.

Hydrogen-bonded organic frameworks (HOFs) have been emerging as a new type of very promising microporous materials for gas separation and purification, but few HOFs structures constructed through hydrogen-bonding tetramers have been explored in this field. Herein, we report the first microporous HOF (termed as HOF-FJU-46) afforded by hydrogen-bonding tetramers with 4-fold interpenetrated diamond networks, which shows excellent chemical and thermal stability. What's more, activated HOF-FJU-46 exhibits the highest xenon (Xe) uptake of 2.51 mmol g-1 and xenon/krypton (Kr) selectivity of 19.9 at the ambient condition among the reported HOFs up to date. Dynamic breakthrough tests confirmed the excellent Xe/Kr separation of HOF-FJU-46a, showing high Kr productivity (110 mL g-1 ) and Xe uptake (1.29 mmol g-1 ), as well as good recyclability. The single crystal X-ray diffraction and the molecular simulations revealed that the abundant accessible aromatic and pyrazole rings in the pore channels of HOF-FJU-46a can provide the multiple strong C-H⋅⋅⋅Xe interactions with Xe atoms.

Multivariate Hydrogen-Bonded Organic Frameworks with Tunable Permanent Porosities for Capture of a Mustard Gas Simulant.

Precise synthesis of topologically predictable and discrete molecular crystals with permanent porosities remains a long-term challenge. Here, we report the first successful synthesis of a series of 11 isoreticular multivariate hydrogen-bonded organic frameworks (MTV-HOFs) from pyrene-based derivatives bearing -H, -CH3 , -NH2 and -F groups achieved by a shape-fitted, π-π stacking self-assembly strategy. These MTV-HOFs are single-crystalline materials composed of tecton, as verified by single-crystal diffraction, nuclear magnetic resonance (NMR) spectra, Raman spectra, water sorption isotherms and density functional theory (DFT) calculations. These MTV-HOFs exhibit tunable hydrophobicity with water uptake starting from 50 to 80 % relative humidity, by adjusting the combinations and ratios of functional groups. As a proof of application, the resulting MTV-HOFs were shown to be capable of capturing a mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES) from moisture. The location of different functional groups within the pores of the MTV-HOFs leads to a synergistic effect, which resulted in a superior CEES/H2 O selectivity (up to 94 %) compared to that of the HOFs with only pure component and enhanced breakthrough performance (up to 4000 min/g) when compared to benchmark MOF materials. This work is an important advance in the synthesis of MTV-HOFs, and provides a platform for the development of porous molecular materials for numerous applications.

Pore Modulation of Hydrogen-Bonded Organic Frameworks for Efficient Separation of Propylene.

Developing hydrogen-bonded organic frameworks (HOFs) that combine functional sites, size control, and storage capability for targeting gas molecule capture is a novel and challenging venture. However, there is a lack of effective strategies to tune the hydrogen-bonded network to achieve high-performance HOFs. Here, a series of HOFs termed as HOF-ZSTU-M (M=1, 2, and 3) with different pore structures are obtained by introducing structure-directing agents (SDAs) into the hydrogen-bonding network of tetrakis (4-carboxyphenyl) porphyrin (TCPP). These HOFs have distinct space configurations with pore channels ranging from discrete to continuous multi-dimensional. Single-crystal X-ray diffraction (SCXRD) analysis reveals a rare diversity of hydrogen-bonding models dominated by SDAs. HOF-ZSTU-2, which forms a strong layered hydrogen-bonding network with ammonium (NH4 + ) through multiple carboxyl groups, has a suitable 1D "pearl-chain" channel for the selective capture of propylene (C3 H6 ). At 298 K and 1 bar, the C3 H6 storage density of HOF-ZSTU-2 reaches 0.6 kg L-1 , representing one of the best C3 H6 storage materials, while offering a propylene/propane (C3 H6 /C3 H8 ) selectivity of 12.2. Theoretical calculations and in situ SCXRD provide a detailed analysis of the binding strength of C3 H6 at different locations in the pearl-chain channel. Dynamic breakthrough tests confirm that HOF-ZSTU-2 can effectively separate C3 H6 from multi-mixtures.

Photo Responsive Electron and Proton Conductivity within a Hydrogen-Bonded Organic Framework.

Rational design of crystalline porous materials with coupled proton-electron transfer has not yet been reported to date. Herein, we report a donor-acceptor (D-A) π-π stacking hydrogen-bonded organic framework (HOF; HOF-FJU-36) with zwitterionic 1,1'-bis(3-carboxybenzyl)-4,4'-bipyridinium (H2 L2+ ) as acceptor and 2,7-naphthalene disulfonate (NDS2- ) as donor to form a two-dimensional (2D) layer. Three water molecules were situated in the channels to connect with acidic species through hydrogen bonding interactions to give a 3D framework. The continuous π-π interactions along the a axis and the smooth H-bonding chain along the b axis provide the electron and proton transfer pathways, respectively. After 405 nm light irradiation, the photogenerated radicals could simultaneously endow HOF-FJU-36 with photoswitchable electron and proton conductivity due to coupled electron-proton transfer. By single-crystal X-ray diffraction (SCXRD) analyses, X-ray photoelectron spectroscopy (XPS), transient absorption spectra and density functional theory (DFT) calculations, the mechanism of the switchable conductivity upon irradiation has been demonstrated.