Nanoscale Metal-Organic Frameworks as a Photoluminescent Platform for Bioimaging and Biosensing Applications.

The tracking of nanomedicines in their concentration and location inside living systems has a pivotal effect on the understanding of the biological processes, early-stage diagnosis, and therapeutic monitoring of diseases. Nanoscale metal-organic frameworks (nano MOFs) possess high surface areas, definite structure, regulated optical properties, rich functionalized sites, and good biocompatibility that allow them to excel in a wide range of biomedical applications. Controllable syntheses and functionalization endow nano MOFs with better properties as imaging agents and sensing units for the diagnosis and treatment of diseases. This minireview summarizes the tunable synthesis strategies of nano MOFs with controllable size, shape, and regulated luminescent performance, and pinpoints their recent advanced applications as optical elements in bioimaging and biosensing. The current limitations and future development directions of nano MOF-contained materials in bioimaging and biosensing applications are also discussed, aiming to expand the biological applications of nano MOF-based nanomedicine and facilitate their production or clinical translation.

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.

Flexible hydrogen-bonded organic frameworks (HOFs): opportunities and challenges.

Flexible behavior is one of the most fascinating features of hydrogen-bonded organic frameworks (HOFs), which represent an emerging class of porous materials that are self-assembled via H-bonding between organic building units. Due to their unique flexibility, HOFs can undergo structural changes or transformations in response to various stimuli (physical or chemical). Taking advantage of this unique structural feature, flexible HOFs show potential in multifunctional applications such as gas storage/separation, molecular recognition, sensing, proton conductivity, biomedicine, etc. While some other flexible porous materials have been extensively studied, the dynamic behavior of HOFs remains relatively less explored. This perspective highlights the inherent flexible properties of HOFs, discusses their different flexible behaviors, including pore size/shape changes, interpenetration/stacking manner, H-bond breaking/reconstruction, and local dynamic behavior, and highlights their potential applications. We believe that this perspective will not only contribute to HOF chemistry and materials science, but will also facilitate the ongoing extensive research on dynamic porous materials.

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.

Pristine MOF Materials for Separator Application in Lithium-Sulfur Battery.

Lithium-sulfur (Li-S) batteries have attracted significant attention in the realm of electronic energy storage and conversion owing to their remarkable theoretical energy density and cost-effectiveness. However, Li-S batteries continue to face significant challenges, primarily the severe polysulfides shuttle effect and sluggish sulfur redox kinetics, which are inherent obstacles to their practical application. Metal-organic frameworks (MOFs), known for their porous structure, high adsorption capacity, structural flexibility, and easy synthesis, have emerged as ideal materials for separator modification. Efficient polysulfides interception/conversion ability and rapid lithium-ion conduction enabled by MOFs modified layers are demonstrated in Li-S batteries. In this perspective, the objective is to present an overview of recent advancements in utilizing pristine MOF materials as modification layers for separators in Li-S batteries. The mechanisms behind the enhanced electrochemical performance resulting from each design strategy are explained. The viewpoints and crucial challenges requiring resolution are also concluded for pristine MOFs separator in Li-S batteries. Moreover, some promising materials and concepts based on MOFs are proposed to enhance electrochemical performance and investigate polysulfides adsorption/conversion mechanisms. These efforts are expected to contribute to the future advancement of MOFs in advanced Li-S batteries.

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.

Hypoxia-Responsive Hydrogen-Bonded Organic Framework-Mediated Protein Delivery for Cancer Therapy.

The efficient delivery of therapeutic proteins to tumor sites is a promising cancer treatment modality. Hydrogen-bonded organic frameworks (HOFs) are successfully used for the protective encapsulation of proteins; however, easy precipitation and lack of controlled release of existing HOFs limit their further application for protein delivery in vivo. Here, a hypoxia-responsive HOF, self-assembled from azobenzenedicarboxylate/polyethylene glycol-conjugated azobenzenedicarboxylate and tetrakis(4-amidiniumphenyl)methane through charge-assisted hydrogen-bonding, is developed for systemic protein delivery to tumor cells. The newly generated HOF platform efficiently encapsulates representative cytochrome C, demonstrating good dispersibility under physiological conditions. Moreover, it can respond to overexpressed reductases in the cytoplasm under hypoxic conditions, inducing fast intracellular protein release to exert therapeutic effects. The strategy presented herein can be applied to other therapeutic proteins and can be expanded to encompass more intrinsic tumor microenvironment stimuli. This offers a novel avenue for utilizing HOFs in protein-based cancer therapy.

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.

A novel hydrophobic carborane-hybrid microporous material for reversed C2H6 adsorption and efficient C2H4/C2H6 separation under humid conditions.

Since ethylene (C2H4) is important feedstock in the chemical industry, developing economical and energy-efficient adsorption separation techniques based on ethane (C2H6)-selective adsorbents to replace the energy-intensive cryogenic distillation is highly demanded, which however remains a daunting challenge. While previous anionic boron cluster hybrid microporous materials display C2H4-selective features, we herein reported that the incorporation of a neutral para-carborane backbone and aliphatic 1,4-diazabicyclo[2.2.2]octane (DABCO) enables the reversed adsorption of C2H6 over C2H4. The generated carborane-hybrid microporous material ZNU-10 (ZNU = Zhejiang Normal University) is highly stable in humid air and maintains good C2H6/C2H4 separation performance under high humidity. Gas loaded single crystal structure and density-functional theory (DFT) calculations revealed that the weakly polarized carborane and DABCO within ZNU-10 induce more specific C-Hδ+⋯Hδ--B dihydrogen bonds and other van der Waals interactions with C2H6, while the suitable pore space allows the high C2H6 uptake. Approximately 14.5 L kg-1 of polymer grade C2H4 can be produced from simulated C2H6/C2H4 (v/v 10/90) mixtures under ambient conditions in a single step, comparable to those of many popular materials.

Switchable Anisotropic/Isotropic Photon Transport in a Double-Dipole Metal-Organic Framework via Radical-Controlled Energy Transfer.

Directional control of photon transport at micro/nanoscale holds great potential in developing multifunctional optoelectronic devices. Here, the switchable anisotropic/isotropic photon transport is reported in a double-dipole metal-organic framework (MOF) based on radical-controlled energy transfer. Double-dipole MOF microcrystals with transition dipole moments perpendicular to each other have been achieved by the pillared-layer coordination strategy. The energy transfer between the double dipolar chromophores can be modulated by the photogenerated radicals, which permits the in situ switchable output on both polarization (isotropy/anisotropy state) and wavelength information (blue/red-color emission). On this basis, the original MOF microcrystal with isotropic polarization state displays the isotropic photon transport and similar reabsorption losses at various directions, while the radical-affected MOF microcrystal with anisotropic polarization state shows the anisotropic photon transport with distinct reabsorption losses at different directions, finally leading to the in situ switchable anisotropic/isotropic photon transport. These results offer a novel strategy for the development of MOF-based photonic devices with tunable anisotropic performance.

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.

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.

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.

Multistate structures in a hydrogen-bonded polycatenation non-covalent organic framework with diverse resistive switching behaviors.

The inherent structural flexibility and reversibility of non-covalent organic frameworks have enabled them to exhibit switchable multistate structures under external stimuli, providing great potential in the field of resistive switching (RS), but not well explored yet. Herein, we report the 0D+1D hydrogen-bonded polycatenation non-covalent organic framework (HOF-FJU-52), exhibiting diverse and reversible RS behaviors with the high performance. Triggered by the external stimulus of electrical field E at room temperature, HOF-FJU-52 has excellent resistive random-access memory (RRAM) behaviors, comparable to the state-of-the-art materials. When cooling down below 200 K, it was transferred to write-once-read-many-times memory (WORM) behaviors. The two memory behaviors exhibit reversibility on a single crystal device through the temperature changes. The RS mechanism of this non-covalent organic framework has been deciphered at the atomic level by the detailed single-crystal X-ray diffraction analyses, demonstrating that the structural dual-flexibility both in the asymmetric hydrogen bonded dimers within the 0D loops and in the infinite π-π stacking column between the loops and chains contribute to reversible structure transformations between multi-states and thus to its dual RS behaviors.

Specific Propyne Trapping Sites within a Robust MOF for Efficient Propyne/Propadiene Separation with Record Propadiene Productivity.

Separating propyne/propadiene to produce pure propadiene is extremely challenging in industry due to their similar properties. Herein, a novel ZrF6 2- anion pillared cage-like metal-organic framework (termed as CuZrF6 -TPA) for highly efficient propyne/propadiene separation is reported. It exhibits high propyne capacity (177.4/188.6 cm3 /cm3 at 0.5/1.0 bar and 298 K), benchmark separation selectivity (6.0), and remarkable separation potential (5.7 mol L-1 ) simultaneously. Record propadiene productivity (≈4.7 mol L-1 ) is achieved through a single adsorption process in breakthrough experiments with excellent recycle stability even under humid conditions. Based on the structure of propyne-loaded single crystals, two binding sites are identified, including a major propyne trapping site at the windows and a minor binding site located in the large cages. Modelling studies further confirm that the contracted cage windows surrounded with rotating Lewis basic F atoms and aromatic rings are the optimal bonding sites to capture propyne with multiple hydrogen bonding and π···π interactions.

Linkage conversions in single-crystalline covalent organic frameworks.

Single-crystal X-ray diffraction is a powerful characterization technique that enables the determination of atomic arrangements in crystalline materials. Growing or retaining large single crystals amenable to it has, however, remained challenging with covalent organic frameworks (COFs), especially suffering from post-synthetic modifications. Here we show the synthesis of a flexible COF with interpenetrated qtz topology by polymerization of tetra(phenyl)bimesityl-based tetraaldehyde and tetraamine building blocks. The material is shown to be flexible through its large, anisotropic positive thermal expansion along the c axis (αc = +491 × 10-6 K-1), as well as through a structural transformation on the removal of solvent molecules from its pores. The as-synthesized and desolvated materials undergo single-crystal-to-single-crystal transformation by reduction and oxidation of its imine linkages to amine and amide ones, respectively. These redox-induced linkage conversions endow the resulting COFs with improved stability towards strong acid; loading of phosphoric acid leads to anhydrous proton conductivity up to ca. 6.0 × 10-2 S cm-1.

Smart-Responsive HOF Heterostructures with Multiple Spatial-Resolved Emission Modes toward Photonic Security Platform.

Luminescent hydrogen-bonded organic frameworks (HOFs) with the unique dynamics and versatile functional sites hold great potential application in information security, yet most of responsive HOFs focus on the single-component framework with restrained emission control, limiting further applications in advanced confidential information protection. Herein, the first smart-responsive HOF heterostructure with multiple spatial-resolved emission modes for covert photonic security platform is reported. The HOF heterostructures are prepared by integrating different HOFs into a single microwire based on a hydrogen-bond-assisted epitaxial growth method. The distinct responsive behaviors of HOFs permit the heterostructure to simultaneously display the thermochromism via the framework transformation and the acidichromism via the protonation effect, thus generating multiple emission modes. The dual stimuli-controlled spatial-resolved emission modes constitute the fingerprint of a heterostructure, and enable the establishment of the smart-responsive photonic barcode with multiple convert states, which further demonstrate the dynamic coding capability and enhanced security in anticounterfeiting label applications. These results offer a promising route to design function-oriented smart responsive HOF microdevices toward advanced anticounterfeiting applications.

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.

Ultrasound programmable hydrogen-bonded organic frameworks for sono-chemogenetics.

The precise control of mechanochemical activation within deep tissues via non-invasive ultrasound holds profound implications for advancing our understanding of fundamental biomedical sciences and revolutionizing disease treatments. However, a theory-guided mechanoresponsive materials system with well-defined ultrasound activation has yet to be explored. Here we present the concept of using porous hydrogen-bonded organic frameworks (HOFs) as toolkits for focused ultrasound programmably triggered drug activation to control specific cellular events in the deep brain, through on-demand scission of the supramolecular interactions. A theoretical model is developed to visualize the mechanochemical scission and ultrasound mechanics, providing valuable guidelines for the rational design of mechanoresponsive materials at the molecular level to achieve programmable and spatiotemporal activation control. To demonstrate the practicality of this approach, we encapsulate designer drug clozapine N-oxide (CNO) into the optimal HOF nanoparticles for FUS gated release to activate engineered G-protein-coupled receptors in the mice and rat ventral tegmental area (VTA), and hence achieved targeted neural circuits modulation even at depth 9 mm with a latency of seconds. This work demonstrates the capability of ultrasound to precisely control molecular interaction and develops ultrasound programmable HOFs to minimally invasive and spatiotemporally control cellular events, thereby facilitating the establishment of precise molecular therapeutic possibilities. We anticipate that this research could serve as a source of inspiration for precise and non-invasive molecular manipulation techniques, potentially applicable in programming molecular robots to achieve sophisticated control over cellular events in deep tissues.