Hydrogen-bonded Framework Research Articles

Single crystalline, Non-stoichiometric Hydrogen-bonded Organic Frameworks Showing Versatile Fluorescence Depending on Composition Ratios and Distributions.

We report on the synthesis, characterization and photobehavior of single crystalline non-stoichiometric hydrogen-bonded organic frameworks (NS-HOFs). NS-HOFs (BTNT-1) with various composition ratios were successfully obtained as single crystals from two analogue tetratopic carboxylic acids, possessing naphthalene and benzothiadiazole cores NTTA and BTTA, respectively. The heterogeneous distribution of the components was thoroughly confirmed by time-resolved fluorescence microscopy and focused synchrotron X-ray radiation techniques, for the first time. The versatile fluorescence of BTNT-1 behavior depends on the composition ratio and distribution of the component in the single crystals. We observed not only fluorescence bands with various colors such as purple, blue, green and white, depending on the composition ratio of both components in BTNT-1, but also different emission bands from a single crystal. Furthermore, we provide details on their emission lifetimes following the composition, emission color and targeted region on the crystal. These results demonstrate unique and versatile optical properties of carboxylic acid-based NS-HOFs and provide a concept of creating functional mixed porous materials capable of different and tunable optical properties.

Magnetically Responsive Enzyme and Hydrogen-Bonded Organic Framework Biocomposites for Biosensing.

The one-pot synthesis of multicomponent hydrogen-bonded organic framework (HOF) biocomposites is reported. The co-immoblization of enzymes and magnetic nanoparticles (MNPs) into the HOF crystals yielded biocatalysts (MNPs-enzyme@BioHOF-1) with dynamic localization properties. Using a permanent magnet, it is possible to separate the MNPs-enzyme@BioHOF-1 particles from a solution. Catalase (CAT) and glucose oxidase (GOx) show increased retention of their activity when coimmobilized with MNPs. MNPs-GOx@BioHOF-1 biocomposites are used to prepare a proof-of-concept glucose microfluidic biosensor, where a magnet allow to position and keep in place the biocomposite inside a microfluidic chip. The magnetic response of these biocatalysts can pave the way for new applications for the emerging HOF biocomposites.

Molecular Assembly in Optical Cavities.

Chemistry has traditionally focused on the synthesis of desired compounds, with organic synthesis being a key method for obtaining target molecules. In contrast, self-assembly -where molecules spontaneously organize into well-defined structures- has emerged as a powerful tool for fabricating intricate structures. Self-assembly was initially studied in biological systems but has been developed for synthetic methods, leading to the field of supramolecular chemistry, where non-covalent interactions/bonds guide molecular assembly. This has led to the development of complex molecular structures, such as metal-organic frameworks and hydrogen-bonded organic frameworks. Parallel to this field, cavity quantum electrodynamics (QED), developed in the mid-20th century, has recently intersected with molecular assembly. Early research in cavity strong coupling focused on inorganic solids and simple molecules, but has since extended to molecular assemblies. The strong coupling synergized with molecular assembly will generate new polaritonic phenomena and applications.

A Microporous Hydrogen-Bonded Organic Framework with Open Pyrene Sites Isolated by Hydrogen-Bonded Helical Chains for Efficient Separation of Xenon and Krypton.

Achieving efficient xenon/krypton (Xe/Kr) separation in emerging hydrogen-bonded organic frameworks (HOFs) is highly challenging because of the lack of gas-binding sites on their pore surfaces. Herein, we report the first microporous HOF (HOF-FJU-168) based on hydrogen-bonded helical chains, which prevent self-aggregation of the pyrene core, thereby preserving open pyrene sites on the pore surfaces. Its activated form, HOF-FJU-168a is capable of separating Xe/Kr under ambient conditions while achieving an excellent balance between adsorption capacity and selectivity. At 296 K and 1 bar, the Xe adsorption capacity of HOF-FJU-168a reached 78.31 cm³/g, with an Xe/Kr IAST selectivity of 22.0; both values surpass those of currently known top-performing HOFs. Breakthrough experiments confirmed its superior separation performance with a separation factor of 8.6 and a yield of high-purity Kr (> 99.5%) of 184 mL/g. Furthermore HOF-FJU-168 exhibits excellent thermal and chemical stability, as well as renewability. Single-crystal X-ray diffraction and molecular modeling revealed that the unique electrostatic surface potential around the open pyrene sites creates a micro-electric field, exerting a stronger polarizing effect on Xe than on Kr, thereby enhancing host-Xe interactions.

Hydrogen-Bonded Organic Framework and Metal-Organic Framework Assembly of Waterwheel PgC-Noria Molecule: Regulating Microstructure Enables Iodine Transfer.

Hydrogen-bonded organic frameworks (HOFs) are a type of crystalline porous materials self-assembled from organic or metal-organic building blocks via intermolecular hydrogen bonding, which have received increasing attention due to their reversible and flexible hydrogen bonding properties. Currently, it remains a challenge to construct HOFs based on complex or porous organic cages as molecular building blocks. Herein, a 3D HOF (PgC-HOF) featuring honeycomb-shaped channels is crafted utilizing a sizable waterwheel-like PgC-noria organic molecule cage. The pivotal role of intermolecular multipoint hydrogen bonding interactions in upholding structural integrity and stability is underscored by the possession of 36 phenolic hydroxyl groups in PgC-HOF. Interestingly, the introduction of calcium ions into the reaction system results in the formation of the metal-organic framework (PgC-MOF), with the channel dimensions increasing from 6.8 to 9.1Å. Furthermore, I2 sorption/release experiments are conducted on PgC-HOF and PgC-MOF, achieving an increase in the optimal adsorption amount from 1.45 to 2.19gg-1 and a transition from an irreversible adsorbent to a reversible adsorbent.

Optimizing Propylene/Propane Sieving Separation through Gate-Pressure Control within a Flexible Organic Framework.

The separation of propylene (C3H6) and propane (C3H8) is of great significance in the chemical industry, which poses a challenge due to their almost identical kinetic diameters and similar physical properties. In this work, we synthesized an ultramicroporous flexible hydrogen-bonded organic framework (named HOF-FJU-106) by using molecule 2,3,6,7-tetra(4-cyanophenyl)tetrathiafulvalene (TTF-4CN). The formation of the dimer causes the TTF-4CN molecular to bend and weaken π-stacked interactions, coupled with the flexibility of C≡N···H-C hydrogen bonds, which leads to reversible conversion between open and closed frameworks through the mutual slip of adjacent layers/columns under activation and stimulation of gas molecules. Through gas adsorption isotherms and adsorption enthalpy, HOF-FJU-106a exhibited adaptive adsorption and stronger binding affinity for C3H6, and presented a recorded gas uptake ratio of C3H6/C3H8 (23.77) among presentative HOF materials at room temperature to date. Importantly, the flexible HOF-FJU-106a shows an interesting phenomenon about the reversible gate pressure control under variable temperature, which realized the gas adsorption and separation performance enhancement for the binary C3H6/C3H8 mixtures. This strategy through designing HOFs with thermoregulatory gating effect is a powerful way to maximize the performance of materials.

A Grafting Hydrogen-bonded Organic Framework for Benchmark Selectivity of C2H2/CO2 Separation under Ambient Conditions.

Reticular chemistry and pore engineering have garnered significant advancements in metal-organic frameworks and covalent organic frameworks, leveraging robust metal-coordination and covalent bonds. However, these achievements remain elusive in hydrogen-bonded organic frameworks, hindered by their inherent weakness in hydrogen bonding. Herein, we strategically manipulate the porosity of hydrogen-bonded frameworks through a grafting approach, culminating in the synthesis of two isomorphic HOFs, HOF-FJU-99 and HOF-FJU-100, with distinct pore environments. Remarkably, HOF-FJU-100, with its microporous architecture, not only showcases exceptional stability but also achieves unparalleled separation efficiency and ultrahigh selectivity for C2H2/CO2 mixtures (50/50, v/v) under ambient conditions. Its IAST selectivity value of 201 stands as a benchmark, towering over all previously reported HOFs. The pore of HOF-FJU-100 boasts an electrostatic potential highly favourable for C2H2 adsorption, as evidenced by single crystal X-ray diffraction analysis revealing multiple hydrogen bonding interactions between C2H2 molecules and the framework. In situ gas-carrier powder X-ray diffraction analysis underscores the adaptability of pore structure, dynamically adjusting its orientation in response to C2H2, thereby enabling a highly efficient and specific separation of C2H2/CO2 mixtures through specific adsorptive interactions.

2D/2D Hydrogen-Bonded Organic Frameworks/Covalent Organic Frameworks S-Scheme Heterojunctions for Photocatalytic Hydrogen Evolution.

Hydrogen-bonded organic frameworks (HOFs) demonstrate significant potential for application in photocatalysis. However, the low efficiency of electron-hole separation and limited stability inhibit their practical utilization in photocatalytic hydrogen evolution from water splitting. Herein, the novel dual-pyrene-base supramolecular HOF/COF 2D/2D S-scheme heterojunction between HOF-H4TBAPy (Py-HOF, H4TBAPy represents the 1,3,6,8-tetrakis (p-benzoic acid) pyrene) and Py-COF was successfully established using a rapid self-assembly solution dispersion method. Experimental and theoretical investigations confirm that the size-matching of two crystalline porous materials enables the integrated heterostructure material with abundant surface reaction sites, strong interaction, and an enhanced S-scheme built-in electric field, thus significantly improving the efficiency of photogenerated charge carrier separation and stability. Notably, the optimal HOF/COF heterojunction achieves a photocatalytic hydrogen evolution rate of 390.68 mmol g-1 h-1, which is 2.28 times higher than that of pure Py-HOF and 9.24 times higher than that of pure COF. These findings precisely acquire valuable atomic-scale insights into the ingenious design of dual-pyrene-based S-scheme heterojunction. This work presents an innovative perspective for forming supramolecular S-scheme heterojunctions over HOF-based semiconductors, offering a protocol for designing the powerful and strong-coupling S-scheme built-in electric fields for efficient solar energy utilization.

High Proton Conductivity of Sulfonate-amine Ionic HOFs and Enhancement of SPEEK Composite Membranes.

Hydrogen-bonded organic frameworks (HOFs) are crystalline materials assembled by intermolecular hydrogen-bonding interactions, and their hydrogen-bonding structures are effective pathways for proton transport. Herein, we synthesize iHOF-45 using 4,4'-diaminodiphenylmethane and 1,3,6,8-pyrenetetrasulfonicacid sodium salt with 2D hydrogen-bonding networks. The stability of ionic HOFs (iHOFs) can be enhanced by introducing ionic bonds in addition to hydrogen-bonding forces. Thermal analyses demonstrated that iHOF-45 exhibited excellent thermal stability up to 332 °C. The proton conductivity of iHOF-45 was evaluated, demonstrating a notable increase with rising temperature and RH. At 100 °C and 98 % RH, the conductivity reached 5.25×10-3 S cm-1. The activation energy (Ea) of iHOF-45 was calculated to be 0.281 eV for 98 % RH, and the proton conduction was attributed to the Grotthuss mechanism, whereby the protons were transported in 2D hydrogen-bonding networks. Moreover, iHOF-45 was doped into SPEEK to prepare composite membranes, the proton conductivity of the 15 % iHOF-45/SPEEK membrane reached 9.52×10-2 S cm-1 at 80 °C and 98 % RH, representing a 45.1 % increase over that of the SPEEK. This suggests that doping enhances the proton conductivity of SPEEK and providing a reference for the development of high proton conductivity materials.

A charge-assisted hydrogen-bonded organic framework with polar porosities for selective separation of o-xylene from C8H10 aromatic isomers

A charge-assisted hydrogen-bonded organic framework with polar porosities for selective separation of o-xylene from C8H10 aromatic isomers

Design of magnetically functionalized hydrogen-bonded organic framework for extraction and enrichment of bisphenols from environmental and human samples

The magnetic functionalized hydrogen bond organic framework named Fe3O4@PFC-11/1 was prepared for the first time and used as sorbent of magnetic solid-phase extraction to enrich bisphenols (BPs) prior to high-performance liquid chromatography analysis. The limits of detection were achieved 0.03–0.07 ng/mL, and the enrichment factors were calculated in the range of 234–296. The adsorption of Fe3O4@PFC-11/1 to BPs can be finished within 10 s. The maximum adsorption capacities of Fe3O4@PFC-11/1 to bisphenol F, bisphenol A, bisphenol B and bisphenol AF were calculated as 249.95, 413.74, 474.38 and 676.06 mg/g, respectively. The main adsorption mechanisms of BPs on Fe3O4@PFC-11/1 are attributed to pore filling, van der Waals force, hydrogen bond and π-π interaction. Finally, BPs were successfully detected in environmental and human samples with satisfactory recoveries (78.2–117.9 %). This work presented combination of Fe3O4 with PFC-1 to obtain a promising magnetic sorbent for extraction and enrichment of trace compounds in complex matrices.

Controllable synthesis of hydrogen-bonded organic framework encapsulated enzyme for continuous production of chiral hydroxybutyric acid in a two-stage cascade microreactor

Constructing a framework carrier to stabilize protein conformation, induce high embedding efficiency, and acquire low mass-transfer resistance is an urgent issue in the development of immobilized enzymes. Hydrogen-bonded organic frameworks (HOFs) have promising application potential for embedding enzymes. In fact, no metal involvement is required, and HOFs exhibit superior biocompatibility, and free access to substrates in mesoporous channels. Herein, a facile in situ growth approach was proposed for the self-assembly of alcohol dehydrogenase encapsulated in HOF. The micron-scale bio-catalytic composite was rapidly synthesized under mild conditions (aqueous phase and ambient temperature) with a controllable embedding rate. The high crystallinity and periodic arrangement channels of HOF were preserved at a high enzyme encapsulation efficiency of 59%. This bio-composite improved the tolerance of the enzyme to the acid-base environment and retained 81% of its initial activity after five cycles of batch hydrogenation involving NADH coenzyme. Based on this controllably synthesized bio-catalytic material and a common lipase, we further developed a two-stage cascade microchemical system and achieved the continuous production of chiral hydroxybutyric acid (R-3-HBA).

Proton Conduction via Water and Ammonia Coordinated Metal Cationic Species in MOF and MHOF Platforms.

Although metal-organic frameworks (MOFs) and metalo hydrogen-bonded organic frameworks (MHOFs) are designed as promising solid-state proton conductors by incorporating various protonic species intrinsically or extrinsically, design and development of such materials by employing the concept of proton conduction through coordinated polar protic solvent is largely unexplored. Herein, we have constructed two proton-conducting materials having different solvent coordinated metal cationic species: In-H2O-MOF, ({[In(H2O)6][In3(Pzdc)6] ⋅ 15H2O}n; H2Pzdc: pyrazine-2,3-dicarboxylic acid) with coordinated water molecules from hexaaquaindium cationic species, and MHOF-4, ([{Co(NH3)6}2(2,6-NDS)2(H2O)2]n; 2,6-H2NDS: 2,6-naphthalenedisulfonic acid) with coordinated ammonia from hexaammoniacobalt cationic species. Interestingly, higher proton conductivity was achieved for In-H2O-MOF (1.5×10-5 S cm-1) than MHOF-4 (6.3×10-6 S cm-1) under the extreme conditions (80 °C and 95 % RH), which could be attributed to enhanced acidity of coordinated water molecules having much lower pKa value than that of coordinated ammonia. Greater charge polarization on hydrogen atoms of In3+-coordinated water molecules than that of Co2+-coordinated ammonia led to the high conductivity of In-H2O-MOF, as evident by quantum chemical studies. Such a comparative study on metal-coordinated protic polar solvents in achieving proton conduction in crystalline solids is yet to be made.

Zincophilic Sites Enriched Hydrogen-bonded Organic Framework as Multifunctional Regulating Interfacial Layers for Stable Zinc Metal Batteries.

To construct an efficient regulating layer for Zn anodes that can simultaneously address the issues of dendritic growth and side reactions is highly demanded for stable zinc metal batteries (ZMBs). Herein, we fabricate a hydrogen-bonded organic framework (HOF) enriched with zincophilic sites as a multifunctional layer to regulate Zn anodes with controlled spatial ion flux and stable interfacial chemistry (MA-BTA@Zn). The framework with abundant H-bonds helps capture H2O and remove the solvated shells on [Zn(H2O)6]2+, leading to suppressed side reactions. The HOF layer also helps form electrolyte-philic surfaces and expose Zn (002) crystal planes which benefit for rapid conduction and uniform deposition of Zn2+, and weakened sides reactions. Additionally, the electrochemically active zincophilic sites (C=O, -NH2 and triazine groups) favor the targeted guidance and penetration of Zn2+ and provide advantageous sites for uniform Zn deposition. High Young's modulus of the HOF layer further contributes to a high interfacial flexibility and stability against Zn plating-associated stress. The MA-BTA@Zn symmetric cells thereby obtain a substantially extended battery life over 1000 h at 4 mA cm-2. The MA-BTA@Zn||Cu half-cell demonstrates a highly reversible Zn stripping/plating process over 1500 cycles with impressive average Coulombic efficiency (CE) of 99.5% at 10 mA cm-2.

In Situ Encapsulation of Atomically Precise Nanoclusters in Reticular Frameworks via Mechanochemical Synthesis.

The combination of atomically precise nanoclusters (APNCs) and reticular frameworks is promising for generating component-specific nanocomposites with emergent properties. However, traditional liquid-phase synthesis often hampers this potential by damaging APNCs and limiting combination diversity. Here, mechanochemical synthesis to explore the encapsulation of diverse oil- and water-soluble APNCs within various reticular frameworks is employed, establishing a database of 21 unique APNC-framework combinations, including metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), hydrogen-bonded organic frameworks (HOFs), and multivariate MOFs. These framework coatings not only spatially immobilize APNCs but also secure their structures, preventing aggregation and degradation while enhancing stability and activity. Encapsulating Au25 in HOFs resulted in a remarkable 315-fold increase in catalytic activity compared to Au25 homogeneous catalyst, highlighting the framework's crucial role in catalytic enhancement. The mechanochemical synthesis strategy facilitates tailored support screening, catering to specific needs, and shows promise for developing multifunctional systems, including enzyme-APNC@frameworks material for cascade reactions.

Mixed Yttrium and Dysprosium Lactates as the First Example of Rare-Earth Hydrogen-Bonded Organic Framework Solid Solutions

Mixed Yttrium and Dysprosium Lactates as the First Example of Rare-Earth Hydrogen-Bonded Organic Framework Solid Solutions

Construction of Highly Porous and Robust Hydrogen-Bonded Organic Framework for High-Capacity Clean Energy Gas Storage.

Development of highly porous and robust hydrogen-bonded organic frameworks (HOFs) for high-pressure methane and hydrogen storage remains a grand challenge due to the fragile nature of hydrogen bonds. Herein, we report a strategy of constructing the double-walled framework to target highly porous and robust HOF (ZJU-HOF-5a) for extraordinary CH4 and H2 storage. ZJU-HOF-5a features a minimized twofold interpenetration with double-walled structure, in which multiple supramolecular interactions are existed between the interpenetrated walls. This structural configuration can notably enhance the framework robustness while maintaining its high porosity, affording one of the highest gravimetric and volumetric surface areas of 3102 m2 g-1 and 1976 m2 cm-3 among the reported HOFs so far. ZJU-HOF-5a thus exhibits an extremely high volumetric H2 uptake of 43.6 g L-1 at 77 K/100 bar and working capacity of 41.3 g L-1 under combined swing conditions (77 K/100 bar→160 K/5 bar), and also impressive methane storage performance with a 5-100 bar working capacity of 187 (or 159) cm3 (STP) cm-3 at 270 K (or 296 K), outperforming most of the reported porous organic materials. Single-crystal X-ray diffraction studies on CH4-loaded ZJU-HOF-5a reveal that abundant supramolecular binding sites combined with ultrahigh porosities account for its high CH4 storage capacities. Combined with high stability, super-hydrophobicity, and easy recovery, ZJU-HOF-5a is placed among the most promising materials for H2 and CH4 storage applications.

Emerging Mixed-Valence Porous Materials.

The development and applications of porous materials have been revolutionized over the past decades. To fine-tune their fascinating behaviors such as charge-transport, magnetic, and catalytic properties, one of the most effective strategies is incorporating mixed valency into the structures. This Concept provides recent progress on emerging crystalline porous materials, namely, metal-organic frameworks, metal-organic polyhedra, covalent organic frameworks, and hydrogen-bonded organic frameworks, where their mixed valency is either intrinsic or postsynthetically induced via an external stimulus. We further highlight the investigation of mixed valency and potential applications, which sheds light on the design and exploitation of mixed-valence crystalline porous materials.

Novel hydrogen-bonded organic frameworks-based coating for fat oil and grease deposition control in the sewer system

Hydrogen-bonded organic frameworks (HOFs) represent an emerging class of porous materials characterized by crystalline frame structures, self-assembled from organic molecules through hydrogen bonding. This study demonstrates that HOFs fragment into small particles while preserving their original structure when dispersed in a polymeric epoxy solution. The intermolecular hydrogen bond structural and electronic properties of the LH4-HOF complex as well as the mechanism of HOF incorporated epoxy were extensively studied using density functional theory. LH4-HOF has a high Langmuir surface area of 2758.3 m2/g and nonlocal density functional theory pore size distributions of 3 A°. This unique solution processability enables the fabrication of coatings with high stability in aqueous systems. Results from a 30-day leaching test under controlled conditions (pH 7, temperature 20 ± 2 °C) indicate that LH4-HOF incorporated epoxy-coated concrete samples exhibited an over 85 % reduction in calcium release compared to uncoated samples, with epoxy-coated samples alone showing a 60 % reduction in calcium leaching. Additionally, the LH4-HOF-incorporated epoxy coating reduced the formation of fats, oils and grease deposits by more than 73 % on the concrete samples. Thus, this novel coating approach offers a sustainable solution with significant potential applications in sewer management.

Bioinspired Photoluminescent "Spider Web" as Ultrafast and Ultrasensitive Airflow-Acoustic Bimodal Sensor for Human-Computer Interaction and Intelligent Recognition.

Nature provides massive biomimetic design inspiration for constructing structural materials with desired performances. Spider webs can perceive vibrations generated by airflow and acoustic waves from prey and transfer the corresponding information to spiders. Herein, by mimicking the perception capability and structure of a spider web, an ultrafast and ultrasensitive airflow-acoustic bimodal sensor (HOF-TCPB@SF) is developed based on the postfunctionalization of hydrogen-bonded organic framework (HOF-TCPB) on silk film (SF) through hydrogen bonds. The "spider web-like" HOF-TCPB@SF possesses light weight and high elasticity, endowing this airflow sensor with superior properties including an ultralow detection limit (DL, 0.0076 m s-1), and excellent repeatability (480 cycles). As an acoustic sensor, HOF-TCPB@SF exhibits ultrahigh sensitivity (105140.77 cps Pa-1 cm-2) and ultralow DL (0.2980 dB), with the greatest response frequency of 375 Hz and the ability to identify multiple sounds. Moreover, both airflow and acoustic sensing processes show an ultrafast response speed (40 ms) and multiangle recognition response (0-180°). The perception mechanisms of airflow and acoustic stimuli are analyzed through finite element simulation. This bimodal sensor also achieves real-time airflow monitoring, speech recognition, and airflow-acoustic interoperability based on human-computer interaction, which holds great promise for applications in health care, tunnel engineering, weather forecasting, and intelligent textiles.