Porous Crystals Research Articles

Tandem Solid‐Solution Phase Post‐Synthetic Modification of Porous Molecular Crystals for In‐Situ Generation of Fluorophores

AbstractConventional synthetic methods of organic luminescent molecules often involve labor‐intensive solution‐phase organic synthesis, which violate the principles of atom‐economic transformation. Post‐synthetic modification (PSM) offers a promising alternative, allowing direct transformation from one fluorophore to another. Although PSM is commonly implemented in extended frameworks, its application in porous molecular crystals remains challenging. Herein, we focus on utilizing porous molecular crystals, specifically tetraphenylethylene‐cored frameworks, as versatile platforms for tandem PSM reactions to customize organic fluorophores. The tailored skeleton design ensures both the formation of porous structures and the occurrence of tandem solid‐solution phase reactions while maintaining the solid state of reactants and products in each step. The inherent non‐covalent bonding nature of the frameworks facilitates processing and characterization, offering unparalleled advantages for porous networks. The accompanying solid‐state fluorescence transition from green to blue and then to green (or yellow) enables real‐time monitoring of tandem reactions and provides intuitive mechanistic insights. This phenomenon is exploited for the facile construction of a dynamic information encryption system using fluorescent quick response codes.

Hierarchically ordered porous carbon crystals for nanoconfined and sustainable fenton oxidation of water pollutants

In this work, we developed a hierarchically multi-faceted ordered porous carbon crystal (HOPC) for generating a favorable chemical microenvironment to intensify both Fe3+ binding and H2O2 utilization efficiency. The confined pore space and surface functionality enable •OH and micropollutants to be concentrated in the pores, thus significantly accelerating pollutant degradation kinetics (0.034 min−1) with reduced chemical consumption (0.081 mM H2O2). Theoretical calculations and in-situ characterizations reveal that both CO and pyrrolic N act as active sites bridging Fe3+, facilitating the transfer of outermost e− from the p-orbital of active sites (O and N) to the d-orbital of iron, effectively reducing Fe3+ to Fe2+ and enhancing the open-circuit potential of HOPC-Fe3+ complexes, as well as facilitating e− extraction from H2O2. For the first time, H2O2 was unveiled to be both an electron donor and acceptor to cooperate with the iron redox cycle for sustainable •OH generation toward fast pollutant decontamination.

Latent porosity of planar tris(phenylisoxazolyl)benzene.

Interest in developing separation systems for chemical entities based on crystalline molecules has provided momentum for the fabrication of synthetic porous materials showing selectivity in molecular encapsulation, such as metal-organic frameworks, covalent organic frameworks, hydrogen-bonded organic frameworks, zeolites, and macrocyclic molecular crystals. Among these, macrocyclic molecular crystals have generated renewed interest for use in separation systems. Selective encapsulation relies on the sizes, shapes, and dimensions of the pores present in the macrocyclic cavities; thus, nonmacrocyclic molecular crystals with high selectivity for molecular encapsulation via porosity-without-pore behaviors have not been studied. Here, we report that planar tris(phenylisoxazolyl)benzene forms porous molecular crystals possessing latent pores exhibiting porosity-without-pore behavior. After exposing the crystals to complementary guest molecules, the latent pores encapsulate cis- and trans-decalin while maintaining the structural rigidity responsible for the high selectivity. The encapsulation via porosity without pores is a kinetic process with remarkable selectivity for cis-decalin over trans-decalin with a cis-/trans-ratio of 96:4, which is confirmed by single-crystal X-ray diffraction and powder X-ray diffraction analyses. Hirshfeld surface analysis and fingerprint plots show that the latent intermolecular pores are rigidified by intermolecular dipole‒dipole and π-π stacking interactions, which determines the remarkable selectivity of molecular recognition.

Porous organic crystals could store hydrogen

Porous organic crystals could store hydrogen

Supramolecular Assembly of Fused Macrocycle-Cage Molecules for Fast Lithium-Ion Transport.

We report a new supramolecular porous crystal assembled from fused macrocycle-cage molecules. The molecule comprises a prismatic cage with three macrocycles radially attached. The molecules form a nanoporous crystal with one-dimensional (1D) nanochannels. The supramolecular porous crystal can take up lithium-ion electrolytes and achieve an ionic conductivity of up to 8.3 × 10-4 S/cm. Structural analysis and density functional theory calculations reveal that efficient Li-ion electrolyte uptake, the presence of 1D nanochannels, and weak interactions between lithium ions and the crystal enable fast lithium-ion transport. Our findings demonstrate the potential of fused macrocycle-cage molecules as a new design motif for ion-conducting molecular crystals.

Influence of textural variability on plastic response of porous crystal embedded in polycrystalline aggregate: A crystal plasticity study

Damage evolution in polycrystalline aggregates is complicated by the intricate interplay of crystallographic orientation of the porous grain and the surrounding anisotropic matrix. Therefore, formulation of design rules and damage models for polycrystalline materials proves daunting due to relative lack of thorough understanding of the underlying heterogeneity at the mesoscale. This work explores the orientation dependent void growth in a porous crystal embedded in an anisotropic polycrystalline matrix with different initial textures. Polycrystalline face-centered cubic based aggregate is simulated within the framework of crystal plasticity finite element method. Porosity is first modeled in the form of a single pre-existing spherical void in the central grain of the randomly oriented polycrystal. One-hundred crystallographic orientations of the central grain in three-dimensional Euler space are analyzed to reveal the orientation dependent trends of the porous grain. To account for textural variability, the analysis is repeated for polycrystals exhibiting preferred textures like Cube, Brass, Copper and Goss. In this manner, interesting orientation dependent trends in basic tenets of void growth like yield strength, coalescence strain and porosity evolution are unraveled across various polycrystalline textures. To account for spatial heterogeneity as well, porosity in the central grain is then re-distributed and the aforementioned analysis is repeated for all the crystallographic orientations of the central grain embedded in polycrystals with different textures. Owing to the large amount of data thus generated, statistical analysis is invoked to identify stimulating trends and key statistical variables governing the strength and toughness. Consequently, a statistical void growth model is also presented by assessing the CP simulation results and identifying suitable distribution function governing the growth of voids in polycrystals. The modeling framework is expected to inform porous plasticity models aimed at capturing damage evolution in porous grains embedded in polycrystalline materials exhibiting topological and crystallographic anisotropy.

Progressive gas adsorption squeezing through the narrow channel of a soft porous crystal of [Co2(4,4′-bipyridine)3(NO3)4]

Reactions of the ternary components of Co2+ ion, 4,4′-bipyridine, and NO3− give several coordination polymers, which are often obtained in mixed phases. Herein, we explore the condition for the selective formation of Co-1D chain and Co-tongue-and-groove coordination polymers and find reversible interconversion pathways between them. The crystal structures of Co-tongue-and-groove in desolvated and two different CO2-adsorbed states show a one-dimensional corrugated channel with small windows through which CO2 is unlikely to pass. Nevertheless, a sufficient amount of CO2 is adsorbed at 195 K. The CO2 molecules are accommodated in the swollen cavity, forcing their way through the seemingly impermeable window of the channel, which we have named squeezing adsorption. The local motion of the ligand of the window frame plays an essential role in the guest permeation, which proves that the tongue-and-groove coordination polymers are essentially locally flexible porous frameworks.

Highly sensitive SERS detection of melamine based on 3D Ag@porous silicon photonic crystal

The stability, reproducibility and engineering of SERS substrate faces a great challenge in melamine SERS assay. In this work, a simple, highly sensitive, stable and cost-efficient SERS detection platform for melamine was established based on its Raman fingerprints spectrum. The Ag@ porous silicon photonic crystal (Ag@PPC) was prepared as the 3D SERS substrate by electrochemical etching and magnetron sputter technology. The main influence factors for the preparation of SERS substrate were investigated in detail. The analytical enhancement factor of the 3D SERS substrate can reach to 2.6 × 108. The 3D SERS detection platform showed a wide linear detection range of 10−4∼10 mg L−1 and a low limit of detection of 0.1 μg L−1 for melamine. Moreover, such detection platform showed good stability, high reproducibility and high recovery rates for melamine. The 3D Ag@PPC SERS substrate can be easily prepared and engineered, displaying a great potential application in food safety field.

Covalent-Organic Frameworks for Selective and Sensitive Detection of Antibiotics from Water.

As the consumption of antibiotics rises, they have generated some negative impacts on organisms and the environment because they are often unable to be effectively degraded, and seeking effective detection methods is currently a challenge. Covalent-organic frameworks (COFs) are new types of crystalline porous crystals created based on the strong covalent interactions between blocked monomers, and COFs demonstrate great potential in the detection of antibiotics from aqueous solutions because of their large surface area, adjustable porosity, recyclability, and predictable structure. This review aims to present state-of-the-art insights into COFs (properties, classification, synthesis methods, and functionalization). The key mechanisms for the detection of antibiotics and the application performance of COFs in the detection of antibiotics from water are also discussed, followed by the challenges and opportunities for COFs in future research.

Effect of sucrose fatty acid ester on crystal growth of carbon dioxide hydrate in aqueous fructose solution

CO2 hydrate is a remarkable candidate for novel solid carbonated foods because of its large gas capacity. This paper reports the effect of surfactants, essential additives in food production, on hydrate crystal growth by visually observing the CO2 hydrate crystal growth in aqueous fructose + sucrose fatty acid ester solution + gaseous CO2 system. Under all thermodynamic conditions, the surfactants affected the crystal growth of CO2 hydrates at liquid/gas interface, while not influencing growth in the liquid bulk phase. Porous hydrate crystals were formed at the liquid/CO2 interface and grew continuously along the reactor wall. The hydrate crystal morphology in liquid bulk phase was not affected by surfactants, changing from polyhedral and polygonal to dendritic shapes as temperature decreased. Discussion is provided on how the observation results can be specifically applied to intensification of hydrate formation process design and evaluation of hydrated food texture.

Theoretical study on the luminescence mechanism of AIEgens based HOFs adsorbing small molecules

The diversity and reversibility of non-covalent interactions give hydrogen-bonded organic frameworks (HOFs) excellent gas adsorption and separation performance. Here we designed and synthesized HOFs based on aggregation-induced emission luminogens (AIEgens) to visualize the adsorption process of HOFs. We focused on the SQ system and its solvated SQ frameworks by different solvent conditions, employing the thermal vibration correlation function rate formalism coupled hybrid quantum mechanics/molecular mechanics protocol, to elucidate the relation between crystal structure and luminescent properties, as well as the specific adsorption ability of porous SQ HOF crystals on acetylene gas. It is found that compare to SQ crystal, the SQ symmetry in cocrystals are improved, and SQ-DCM cocrystal has the best symmetry. The absorption spectra of five SQ-based crystals are close to each other, and their emission spectra blueshifted from 540 nm of SQ, to 509 nm, 508 nm, 507 nm of SQ-EA, SQ-ACN, SQ-DCM, and then to 495 nm of SQ-TOL, consistent with experimental results. The kic of solvated cocrystals are about 1∼2 orders of magnitude smaller than that of non-solvated crystal SQ, resulting in significantly higher Φexp of solvated cocrystals than that of un-solvated one. DCM with small volume and C2v point group is more suitable for SQ crystal channel, indicating that small free region and shape matching are the key factors affecting the reversibility of crystallization of porous frames during solvent transport. Finally, the volume of the adsorbed gas C2H2 which is close to DCM, is more easily adsorbed by SQ framework. Our study offers theoretical insights into the design of porous crystals for gas adsorption and separation applications.

Tandem Solid-Solution Phase Post-Synthetic Modification of Porous Molecular Crystals for In-Situ Generation of Fluorophores.

Conventional synthetic methods of organic luminescent molecules often involve labor-intensive solution-phase organic synthesis, which violate the principles of atom-economic transformation. Post-synthetic modification (PSM) offers a promising alternative, allowing direct transformation from one fluorophore to another. Although PSM is commonly implemented in extended frameworks, its application in porous molecular crystals remains challenging. Herein, we focus on utilizing porous molecular crystals, specifically tetraphenylethylene-cored frameworks, as versatile platforms for tandem PSM reactions to customize organic fluorophores. The tailored skeleton design ensures both the formation of porous structures and the occurrence of tandem solid-solution phase reactions while maintaining the solid state of reactants and products in each step. The inherent non-covalent bonding nature of the frameworks facilitates processing and characterization, offering unparalleled advantages for porous networks. The accompanying solid-state fluorescence transition from green to blue and then to green (or yellow) enables real-time monitoring of tandem reactions and provides intuitive mechanistic insights. This phenomenon is exploited for the facile construction of a dynamic information encryption system using fluorescent quick response codes.

Flexible Metal-Organic Frameworks: From Local Structural Design to Functional Realization.

ConspectusFlexible metal-organic frameworks (MOFs), also known as soft porous crystals, exhibit dynamic behaviors in response to external physical and chemical stimuli such as light, heat, electric or magnetic field, or the presence of particular matters, on the premise of maintaining their crystalline state. The reversible structural transformation of flexible MOFs, a unique characteristic seldomly found in other types of known solid-state materials, affords them distinct properties in the realms of molecule separation, optoelectronic devices, chemical sensing, information storage, biomedicine applications, and so on. The mechanisms underlying their dynamic behaviors can be comprehensively investigated at the molecular level by means of in situ single-crystal or powder X-ray diffraction as well as other in situ spectroscopic techniques due to the high regularity of these crystalline materials during stimuli-responsive phase transitions. Through the introduction of specific stimuli-responsive groups/moieties into the well-defined and ordered molecular arrays, targeted applications can be achieved, and the performance of flexible MOFs can also be further improved via rational structural design.In this Account, we summarize our progress on the design, synthesis, and applications of flexible MOFs over the past few years. First, we highlight the construction principle of flexible MOFs, emphasizing the pivotal role of local structural design. Using an F-modified ligand, a flexible MOF with remarkable structural transformations can be obtained; the regulation of the metal coordination environment and interpenetrating frameworks is also crucial for achieving flexible MOFs. We also propose a strong correlation strategy based on the supramolecular interactions between the guest molecules and the framework, which realizes the temperature-responsive dynamic spatial "open-closed" regulation. Mechanisms of the dynamic behaviors investigated by the in situ techniques were also presented for the obtained materials. Second, some representative specific applications of the newly developed dynamic coordination systems were reviewed. The gas molecule responsive flexible MOFs show efficient short-chain alkane separation properties with discriminatory sorption behavior toward similar gaseous substrates. Smart sensing of temperature, pressure, and volatile organic compounds was achieved by several novel flexible fluorescent MOFs, with optimization potential through state-of-the-art chemical design. Furthermore, multiferroic materials with multiple bistable states and high working temperatures were also obtained based on flexible MOFs.Finally, we provide a discussion of the challenges of flexible MOFs in future research, including precise and efficient synthesis, in-depth structure-property relationship investigation, performance optimization, and industrialization. We hope that this Account will stimulate further research interest in developing next-generation smart materials based on flexible MOFs for applications in challenging chemical separation, extreme environmental sensing, massive information storage, and beyond.

Three-dimensional reconstruction of porous CeO2 single crystal for effective electrolysis of carbon dioxide

In the quest for long-lasting energy alternatives, solid oxide electrolysers have become a crucial technology in facilitating the transformation of CO2 toward fuels and valuable chemicals. This study proposes a unique method for the catalytic reduction of carbon dioxide at the cathode using porous CeO2 single-crystal electrodes in a solid oxide electrolyser, utilizing temperatures from an industrial waste heat stream. The fluxes and chemical states of oxygen-containing species evolved from the cathode were identified and designed, and the catalytic process of CO2 reduction to CO was effectively regulated by the oxygen-containing species (lattice oxygen, oxygen vacancies and adsorbed oxygen). The results show that the CO yield can reach 6.05 mL min−1 cm−1 with porous (111) CeO2 single crystal as the cathode at 850 °C and 1.8 V. The solid oxide electrolyser exhibits remarkable stability even after 100 h of continuous operation.

Structure Evolution of 2D Covalent Organic Frameworks Unveiled by Single-Crystal X-ray Diffraction.

We report 9 crystal structures of a two-dimensional (2D) covalent organic framework (COF), including the parent Py-1P, 5 derivatives formed by chemical reactions, and 3 dynamic states by solvent exchange/loss. Structure details of these porous crystals, including stacking mode, interlayer distance, pore aperture, and incline angle, before, during, and after conversion processes in solution, were unveiled by single-crystal X-ray diffraction with resolutions up to 0.85 Å. The structure evolution is triggered by stepwise conformational transformation of the molecular building blocks in 2D COF, while their long-range ordering remained unsacrificed.

Real-time observation of a metal complex-driven reaction intermediate using a porous protein crystal and serial femtosecond crystallography

Determining short-lived intermediate structures in chemical reactions is challenging. Although ultrafast spectroscopic methods can detect the formation of transient intermediates, real-space structures cannot be determined directly from such studies. Time-resolved serial femtosecond crystallography (TR-SFX) has recently proven to be a powerful method for capturing molecular changes in proteins on femtosecond timescales. However, the methodology has been mostly applied to natural proteins/enzymes and limited to reactions promoted by synthetic molecules due to structure determination challenges. This work demonstrates the applicability of TR-SFX for investigations of chemical reaction mechanisms of synthetic metal complexes. We fix a light-induced CO-releasing Mn(CO)3 reaction center in porous hen egg white lysozyme (HEWL) microcrystals. By controlling light exposure and time, we capture the real-time formation of Mn-carbonyl intermediates during the CO release reaction. The asymmetric protein environment is found to influence the order of CO release. The experimentally-observed reaction path agrees with quantum mechanical calculations. Therefore, our demonstration offers a new approach to visualize atomic-level reactions of small molecules using TR-SFX with real-space structure determination. This advance holds the potential to facilitate design of artificial metalloenzymes with precise mechanisms, empowering design, control and development of innovative reactions.

Enzyme-Immobilized Porous Crystals for Environmental Applications.

Developing efficient technologies to eliminate or degrade contaminants is paramount for environmental protection. Biocatalytic decontamination offers distinct advantages in terms of selectivity and efficiency; however, it still remains challenging when applied in complex environmental matrices. The main challenge originates from the instability and difficult-to-separate attributes of fragile enzymes, which also results in issues of compromised activity, poor reusability, low cost-effectiveness, etc. One viable solution to harness biocatalysis in complex environments is known as enzyme immobilization, where a flexible enzyme is tightly fixed in a solid carrier. In the case where a reticular crystal is utilized as the support, it is feasible to engineer next-generation biohybrid catalysts functional in complicated environmental media. This can be interpreted by three aspects: (1) the highly crystalline skeleton can shield the immobilized enzyme against external stressors. (2) The porous network ensures the high accessibility of the interior enzyme for catalytic decontamination. And (3) the adjustable and unambiguous structure of the reticular framework favors in-depth understanding of the interfacial interaction between the framework and enzyme, which can in turn guide us in designing highly active biocomposites. This Review aims to introduce this emerging biocatalysis technology for environmental decontamination involving pollutant degradation and greenhouse gas (carbon dioxide) conversion, with emphasis on the enzyme immobilization protocols and diverse catalysis principles including single enzyme catalysis, catalysis involving enzyme cascades, and photoenzyme-coupled catalysis. Additionally, the remaining challenges and forward-looking directions in this field are discussed. We believe that this Review may offer a useful biocatalytic technology to contribute to environmental decontamination in a green and sustainable manner and will inspire more researchers at the intersection of the environment science, biochemistry, and materials science communities to co-solve environmental problems.

Facile fabrication of recyclable robust noncovalent porous crystals from low-symmetry helicene derivative

Porous frameworks constructed via noncovalent interactions show wide potential in molecular separation and gas adsorption. However, it remains a major challenge to prepare these materials from low-symmetry molecular building blocks. Herein, we report a facile strategy to fabricate noncovalent porous crystals through modular self-assembly of a low-symmetry helicene racemate. The P and M enantiomers in the racemate first stack into right- and left-handed triangular prisms, respectively, and subsequently the two types of prisms alternatively stack together into a hexagonal network with one-dimensional channels with a diameter of 14.5 Å. Remarkably, the framework reveals high stability upon heating to 275 °C, majorly due to the abundant π-interactions between the complementarily engaged helicene building blocks. Such porous framework can be readily prepared by fast rotary evaporation, and is easy to recycle and repeatedly reform. The refined porous structure and enriched π-conjugation also favor the selective adsorption of a series of small molecules.

Social Self-Sorting of Quasi-Racemates: A Unique Approach for Dual-Pore Molecular Crystals.

Despite recent advances in porous organic molecular crystals, the engineering of dual-pore systems within the intermolecular voids remains a significant challenge. In this study, we have achieved the crystallization-induced social self-sorting of "quasi-racemic" dialdehydes into a macrocyclic imine. X-ray crystallographic analysis unambiguously characterizes the resulting structure as incorporating two quasi-racemate pairs with four diamine molecules. Notably, different alkyl substituents on the quasi-racemates afford two types of one-dimensional pores within the macrocyclic imine crystal. The different adsorption properties of these pores were substantiated through adsorption experiments. An intriguing helical arrangement of guest molecules was observed within one of the pores. This study provides pioneering evidence that the social self-sorting of quasi-racemates offers a new methodology for creating dual-functional supramolecular materials.

Porous Crystalline Materials Based on Tetrathiafulvalene and Its Analogues: Assembly, Charge Transfer, and Applications.

ConspectusThe directed synthesis and functionalization of porous crystalline materials pose significant challenges for chemists. The synergistic integration of different functionalities within an ordered molecular material holds great significance for expanding its applications as functional materials. The presence of coordination bonds connected by inorganic and organic components in molecular materials can not only increase the structural diversity of materials but also modulate the electronic structure and band gap, which further regulates the physical and chemical properties of molecular materials. In fact, porous crystalline materials with coordination bonds, which inherit the merits of both organic and inorganic materials, already showcase their superior advantages in optical, electrical, and magnetic applications. In addition to the inorganic components that provide structural rigidity, organic ligands of various types serve as crucial connectors in the construction of functional porous crystalline materials. In addition, redox activity can endow organic linkers with electrochemical activity, thereby making them a perfect platform for the study of charge transfer with atom-resolved single-crystal structures, and they can additionally serve as stimuli-responsive sites in sensor devices and smart materials.In this Account, we introduce the synthesis, structural characteristics, and applications of porous crystalline materials based on the famous redox-active units, tetrathiafulvalene (TTF) and its analogues, by primarily focusing on metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). TTF, a sulfur-rich conjugated molecule with two reversible and easily accessible oxidation states (i.e., radical TTF•+ cation and TTF2+ dication), and its analogues boast special electrical characteristics that enable them to display switchable redox activity and stimuli-responsive properties. These inherent properties contribute to the enhancement of the optical, electrical, and magnetic characteristics of the resultant porous crystalline materials. Moreover, delving into the charge transfer phenomena, which is key for the electrochemical process within these materials, uncovers a myriad of potential functional applications. The Account is organized into five main sections that correspond to the different properties and applications of these materials: optical, electrical, and magnetic functionalities; energy storage and conversion; and catalysis. Each section provides detailed discussions of synthetic methods, structural characteristics, the physical and chemical properties, and the functional performances of highlighted examples. The Account also discusses future directions by emphasizing the exploration of novel organic units, the transformation between radical cation TTF•+ and dication TTF2+, and the integration of multifunctionalities within these frameworks to foster the development of smart materials for enhanced performance across diverse applications. Through this Account, we aim to highlight the massive potential of TTF and its analogues-based porous crystals in chemistry and material science.