Properties Of Covalent Organic Frameworks Research Articles

Branched-Chain-Induced Host-Guest Assembly in Covalent-Organic Frameworks for Efficient Separation of No-Carrier-Added 177Lu.

No-carrier-added (NCA) 177Lu is one of the most interesting nuclides for endoradiotherapy. With the dramatically rapid development of radiopharmaceutical and nuclear medicine, there is a sharp increase in the radionuclide supply of NCA 177Lu, which has formed a great challenge to current radiochemical separation constituted on classical materials. Hence, it is of vital importance to design and prepare new functional materials able of recovering 177Lu from an irradiated target with excellent efficacy. In this work, we proposed to apply noncovalent interactions to regulate the porous properties of covalent organic frameworks (COFs) by tuning the branched chain, rendering related covalent hosts different encapsulation abilities toward a flexible guest, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (P507). More interestingly, we found that the noncovalent interaction has a great effect on the host-guest complexes, which can achieve efficient NCA 177Lu separation with high recovery (95.97%). A systematic mechanism combined with experimental and theoretical investigations has confirmed that the noncovalent interactions between COFs and P507 play a preeminent role in adjusting the macroscopic properties of the host-guest complexes. This work not only uncovers that noncovalent interactions can affect the basic properties of covalent organic bonded materials but also provides a strategy for the design and preparation of other new moieties with specific functionalities.

Intuitive and Efficient Approach to Determine the Band Structure of Covalent Organic Frameworks from Their Chemical Constituents.

The optical, electronic, and (photo) catalytic properties of covalent organic frameworks (COFs) are largely determined by their electronic structure and, specifically, by their Frontier conduction and valence bands (VBs). In this work, we establish a transparent relationship between the periodic electronic structure of the COFs and the orbital characteristics of their individual molecular building units, a relationship that is challenging to unravel through conventional solid-state calculations. As a demonstration, we applied our method to five COFs with distinct framework topologies. Our approach successfully predicts their first-principles conduction and VBs by expressing them as a linear combination of the Frontier molecular orbitals localized on the COF fragments. We demonstrate that our method allows for the rapid exploration of the impact of chemical modifications on the band structures of COFs, making it highly suitable for further application in the quest to discover new functional materials.

Carboxyl-functionalized magnetic amide-linked covalent organic framework for efficient extraction of multi-class mycotoxins from soybeans prior to HPLC-MS/MS analysis

Mycotoxins co-contamination in soybean poses great risks to human health, however, due to their diverse structures, it is difficult to simultaneously extract and detect these multi-mycotoxins. By incorporating modification of hydrophilic carboxyl groups with the hydrophobic properties of covalent organic frameworks, a stable cubic carboxyl-functionalized magnetic amide-linked covalent organic framework were fabricated, characterized and utilized as adsorbents for magnetic solid phase extraction (MSPE) of eleven frequently detected mycotoxins from soybeans followed by HPLC-MS/MS analysis. The key MSPE parameters were screened using the Plackett-Burman design and optimized with the Box-Behnken design for response surface methodologies. Under the optimal experimental conditions, the linear range was 0.2–50 μg/kg, the limits of detection were 0.1–1.4 μg/kg. The established method was applied for the soybean analysis with satisfactory recoveries (70.8–108.3%) and precision (intra- and inter-relative standard deviations of 2.1–9.2% and 1.6–11.1%, respectively). With proper modification, this method may have great application potential for simultaneously analyzing and monitoring the multi-mycotoxin contamination in foods to ensure consumer safety and public health.

Gradually Tuning the Flexibility of Two‐Dimensional Covalent Organic Frameworks via Stepwise Structural Transformation and Their Flexibility‐Dependent Properties

AbstractFlexible covalent organic frameworks (COFs) are intriguing for their dynamic properties distinctive from rigid counterparts but still suffer from limited accessibility. Especially, controlling flexibility of COFs is challenging and the impact of different flexibility on properties of COFs has rarely been unveiled. This article reports stepwise adjustment on flexibility of two‐dimensional COFs, which is realized by the designed synthesis of rigid COF (R‐COF), semi‐flexible COF (SF‐COF), and flexible COF (F‐COF) through polymerization, linker exchange, and linkage conversion with a newly developed method for reduction of hydrazone, respectively. Significant difference in breathing behavior and self‐adaptive capability of the three COFs are uncovered through vapor response and iodine capture experiments. Gas sorption experiments indicate that the porosity of F‐COF could switch from “close” state in nitrogen to “open” state in carbon dioxide, which are not observed for R‐COF and SF‐COF. This study not only develops a strategy to adjust the flexibility of COFs by tuning their linkers and linkages, but also provides a deep insight into the impact of different flexibility on properties of COFs, which lays a foundation for the development of this new class of dynamic porous materials.

Gradually Tuning the Flexibility of Two-Dimensional Covalent Organic Frameworks via Stepwise Structural Transformation and Their Flexibility-Dependent Properties.

Flexible covalent organic frameworks (COFs) are intriguing for their dynamic properties distinctive from rigid counterparts but still suffer from limited accessibility. Especially, controlling flexibility of COFs is challenging and the impact of different flexibility on properties of COFs has rarely been unveiled. This article reports stepwise adjustment on flexibility of two-dimensional COFs, which is realized by the designed synthesis of rigid COF (R-COF), semi-flexible COF (SF-COF), and flexible COF (F-COF) through polymerization, linker exchange, and linkage conversion with a newly developed method for reduction of hydrazone, respectively. Significant difference in breathing behavior and self-adaptive capability of the three COFs are uncovered through vapor response and iodine capture experiments. Gas sorption experiments indicate that the porosity of F-COF could switch from "close" state in nitrogen to "open" state in carbon dioxide, which are not observed for R-COF and SF-COF. This study not only develops a strategy to adjust the flexibility of COFs by tuning their linkers and linkages, but also provides a deep insight into the impact of different flexibility on properties of COFs, which lays a foundation for the development of this new class of dynamic porous materials.

Wavelength-Dependent Excitonic Properties of Covalent Organic Frameworks Explored by Theory and Experiments

Many aspects of the correlation between the physical structure, light harvesting, and excitonic properties of covalent organic frameworks (COFs) remain unclear despite being key properties determining their photocatalytic function. One area of COF research that could bring clarity is using both electronic structure theory and time-resolved spectroscopic analysis over a series of systematically varied COFs. Here, we show structure–property relationships between four imine COFs built from a combination of ditopic and tritopic monomers using transient absorption spectroscopy together with time-dependent density functional theory. We find that monomer selection only moderately affects the charge transfer (CT) behavior of the COFs. Instead, we infer that imine chemistry profoundly impacts CT by acting as a CT mediator. Moreover, we discover two distinct valence bands arising from varying degrees of locally excited/CT mixing, which is responsible for energy-dependent exciton dynamics. Finally, we use theory to hypothesize that interlayer interactions can modify excitonic properties that we correlate with tail states commonly observed but rarely investigated in COFs. These results reveal that imine chemistry should be recognized as a very important factor to consider in the development of COF photocatalysts and the correlation of their structural environment with light-harvesting and CT properties that should ultimately determine their photocatalytic function.

Less-precious nitrogen-rich covalent organic frameworks capable of effective rare earth recovery from water

The development of stable and inexpensive adsorbents for La(III) recovery from wastewater is of great importance for rare earth industries. In this work, two novel N-rich covalent organic frameworks (COFs) synthesized via a one-step solvothermal method were termed as COF-PA-CC and COF-ML-CC, and employed as the adsorbents for removal of rare earth (RE) ions from aqueous solution. The structures and properties of COFs were characterized with X-ray diffractometer, total reflection infrared spectrometer, field-emission scanning electron microscopy, X-ray photoelectron spectroscopy, nitrogen adsorption–desorption instrument and thermogravimetric analyzer. The results revealed that COF-PA-CC composed of nanowires with the average length of 500 nm, whereas COF-ML-CC displayed the spherical morphology with the diameter of 100 ∼ 300 nm. Specific surface areas of COF-PA-CC and COF-ML-CC were calculated to be 82.13 and 191.08 m2/g, respectively. The adsorption process of La(III) was well-fitted with pseudo-second-order kinetic model and Langmuir isotherm model, exhibiting the high adsorption capacities of 150.88 and 168.19 mg/g for COF-PA-CC and COF-ML-CC after 120 min. Moreover, the influences of pH, temperature, different RE ions on adsorption performances were comprehensively tested, yielding an optimal adsorption condition (pH = 5.5, 65 °C and 120 min) and a better affinity for some light RE ions. Importantly, the fabricated COFs possess the excellent reusability after five adsorption-regeneration cycles, remaining 97.84 % and 95.51 % of initial capacities for COF-PA-CC and COF-ML-CC, respectively. The adsorption mechanism revealed that the complexation interaction between La(III) and the unoccupied N sites of N-rich COFs was recommended to interpret the remarkable adsorption performance of La(III) on the basis of the characterization analysis after the adsorption with elemental mapping, EDS and XPS. Consequently, these low-cost and robust COFs with abundant active N sites supplied a promising strategy for the recovery of RE ions from wastewater.

Nonlinear optical properties of porphyrin-based covalent organic frameworks determined by steric-orientation of conjugation

The influences of conjugation on the third-order nonlinear optical (NLO) properties of covalent organic frameworks (COFs) provide guidelines to design the structures for desired applications.

Thiol-grafted covalent organic framework-based electrochemical platforms for sensitive detection of Hg(II) ions.

Triazine-based covalent organic frameworks functionalized by thiol and thioether (COFS-CH3/COFS-SH) were designed and served as a platform that could bind with mercury ions specifically based on Hard-Soft-Acid-Base theory. As such, when employing COFs as a modifier in a carbon paste electrode (CPE), the COFS-CH3-modified CPE revealed an extraordinary performance (detection limit of 0.01 ppb; linear range of 0.1 to 1.0 ppb) and repeatability for electrochemical detection of trace mercury, even in real samples collected from tap or lake water. This innovative approach leverages the inherent properties of covalent organic frameworks (COFs) to enable highly sensitive and selective detection of target analytes.

Mimicking Enzymatic Non-Covalent Interactions with Functionalized Covalent Organic Frameworks for Improved Adsorption and Hydrolysis of Cellobiose.

Tuning catalytic centers in heterogeneous catalyst, both in a chemical and a spatial manner, is a powerful approach to improve the stability and the efficiency of catalysts. While the chemical aspects are largely understood, the spatial interactions around active sites, comprised of non-covalent interactions, are difficult to maintain and challenging to study. Herein, the unique properties of covalent organic frameworks (COFs) are utilized to establish an ideal reaction environment for the hydrolysis of cellobiose and other common disaccharides in mild, metal-free, and neutral aqueous conditions. The chosen COF, HCl-PSA-IM-COF-OMe ("HCl" for hydrochloric acid, "PSA" for propyl sulfonic acid, "IM" for imidazole, and "OMe" for methoxy), is modified to be ultra-stable in aqueous conditions and possesses sulfonic acid groups for general acid catalysis and for enhanced hydrogen bonding with reactants as well as intraporous chloride anions for oxocarbenium intermediate stabilization. In addition, the system also relies on the differences in adsorptive binding behavior, Kads , of the reactants and the products to the functionalized framework and benefits from a separate physical, kinetic process to boost the catalytic cycle. Due to its stability in aqueous conditions, HCl-PSA-IM-COF-OMe can be recycled and maintains its hydrolytic properties for five cycles before regeneration is needed.

Cyano Substituent on the Olefin Linkage: Promoting Rather than Inhibiting the Performance of Covalent Organic Frameworks

It is generally believed that the electron-withdrawing cyano group in the olefin linkage would inhibit the stability and π-conjugation of covalent organic frameworks (COFs), which raises concerns about their optoelectronic properties. However, the structure–activity relationship between the structure of olefin linkages and properties of COFs is still inconclusive. In this work, imine-, vinylene-, and acrylonitrile-linked COFs with identical triphenyltriazine building blocks were designed and synthesized. Our work demonstrated that construction of acrylonitrile linkages not only enhanced the chemical stability and photostability but also led to remarkable optoelectronic properties with a record fluorescence quantum yield of 35.37% in the solid state. Further, the acrylonitrile linkage endows TTAN-COF/Pt NPs with superior and durable photocatalytic activity in both the hydrogen evolution reaction (11.94 mmol g–1 h–1; BET surface area, 739.28 m2 g–1) and aerobic oxidation reaction. This work demonstrates that the acrylonitrile linkage can significantly enhance the optoelectronic properties and photocatalytic activities of COFs compared with the highly π-conjugated vinylene linkage, providing a valuable reference for the design of optoelectronic functional materials.

Covalent Organic Frameworks for Electrochemical Sensors: Recent Research and Future Prospects

Background: In recent years, electrochemical sensors are widely preferred because of their high sensitivity, rapid response, low cost and easy miniaturization. Covalent organic frameworks (COFs), a porous crystalline polymer formed by organic units connected by covalent bonds, have been widely used in gas adsorption and separation, drug transportation, energy storage, photoelectric catalysis, electrochemistry and other aspects due to their large specific surface, excellent stability, high inherent porosity, good crystallinity as well as structural and functional controllability. The topological structure of COFs can be designed in advance, the structural units and linkage are diversified, and the structure is easy to be functionalized, which are all beneficial to their application in electrochemical sensors. Methods: The types, synthesis methods, properties of covalent organic frameworks and some examples of using covalent organic frameworks in electrochemical sensors are reviewed. Results: Due to their characteristics of a large specific surface, high porosity, orderly channel and periodically arranged π electron cloud, COFs are often used to immobilize metal nanoparticles, aptamers or other materials to achieve the purpose of building electrochemical sensors with high sensitivity and good stability. Since the structure of COFs can be predicted, different organic units can build COFs with different structures and properties. Therefore, organic units with certain functional groups can be selected to build COFs with certain properties and used directly for electrochemical sensors. Conclusion: COFs have a good application prospect in electrochemical sensors.

Covalent Organic Frameworks Doped with Different Ratios of OMe/OH as Fluorescent and Colorimetric Sensors.

Improving the luminescence properties of covalent organic frameworks (COFs) has always been an important issue. Here, a series of COFs (([OMe]x -TzDa (TzDa is composed only by monomerics Tz and Da, OMe represents the incorporation of monomeric Dm)) with different ratios of OMe and OH were designed and synthesized. The photochemical behavior of [OMe]x -TzDa changed significantly due to the synergistic effect of aggregation induced emission (AIE), intramolecular charge transfer (ICT), and excited-state intramolecular proton transfer (ESIPT) effects. [OMe]2 -TzDa, which contained a ratio of 2/1 of OMe/OH, showed the strongest fluorescence emission in water and the best linear relationship for the detection of pH. Furthermore, [OMe]2 -TzDa was used to monitor HCl and NH3 gases and showed a color change, visible to the naked eye. Therefore, a "confidential pigment" was successfully made. Moreover, [OMe]2 -TzDa was also applied to detect N2 H4 . The work indicates the [OMe]2 -TzDa can serve as the first fluorescence sensor to detect pH, HCl and NH3 gases, which also shows a good response to N2 H4 .

Tunability of the Electronic Properties of Covalent Organic Frameworks

Research on carbon-based covalent organic frameworks (COFs) is a fascinating area in the field of material science due to their excellent performance and broad range of applications in technology. ...

Electronic and Optical Properties of Protonated Triazine Derivatives

The peculiar electronic and optical properties of covalent organic frameworks (COFs) are largely determined by protonation, a ubiquitous phenomenon in the solution environment in which they are synthesized. The resulting effects are non-trivial and appear to be crucial for the intriguing functionalities of these materials. In the quantum-mechanical framework of time-dependent density-functional theory, we investigate from first principles the impact of protonation of triazine and amino groups in molecular building blocks of COFs in water solution. In all considered cases, we find that proton uptake leads to a gap reduction and to a reorganization of the electronic structure, driven by the presence of the proton and by the electrostatic attraction between the positively charged protonated species and the negative counterion in its vicinity. Structural distortions induced by protonation are found to play only a minor role. The interplay between band-gap renormalization and exciton binding strength determines the energy of the absorption onsets: when the former prevails on the latter, a red-shift is observed. Furthermore, the spatial and energetic rearrangement of the molecular orbitals upon protonation induces a splitting of the lowest-energy peaks and a decrease of their oscillator strength in comparison with the pristine counterparts. Our results offer quantitative and microscopic insight into the role of protonation on the electronic and optical properties of triazine derivatives as building blocks of COFs. As such, they contribute to rationalize the relationships between structure, property, and functionality of these materials.

Theoretical Study of Thermoelectric Properties of Covalent Organic Frameworks with Slipped Arrangement

In this study, Density Functional Theory and the Boltzmann transport equation are applied to calculate the semiclassical thermoelectric transport properties of phthalocyanine (PC) covalent organic frameworks with different central metals in the macrocycle MPc-COFs, (M = Co, Cu, and Zn), which have a slipped-AA stacking of 2D polymer sheets. The weakening of π-π stacking increased the role of in-plane intramolecular through-bond carrier transfer involving σ/π interactions, leading to significant anisotropy of transport coefficients in the studied compounds, which are also affected by the nature of the transition metals. The maximum values of thermopower for Co-Pc COF (770 μV/K) and Cu-Pc COF (− 423 μV/K) were found along the in-plane direction. However, for ZnPc-COF, the maximum positive value of the Seebeck coefficient (156 μV/K) was found along the stacking direction, while the maximum value of the thermopower along the in-plane direction was equal to − 315 μV/K. The electronic fitness function was calculated to estimate the thermoelectric performance of the studied compounds for both p- and n-type doping at 300 and 800 K. The maximum values of the electronic fitness function are observed for Cu-Pc and Zn-Pc COFs along the stacking direction at 800 K for both p- and n-type doping, while for p-doped Co-Pc COF the maximum value of this function was found along the in-plane direction.

The luminescent and photophysical properties of covalent organic frameworks.

Covalent organic frameworks (COFs) are an emerging class of crystalline porous polymers that have attracted significant attention due to their tunable properties and structural robustness. As a result, COFs with luminescent properties are of great interest for fields such as chemical sensing, solid-state light emitters, photocatalysis, and optoelectronics. However, the bottom-up synthesis of luminescent COF systems remains a challenge in the field due to an abundance of competing non-radiative pathways, including phenomena such as aggregate caused quenching (ACQ). To overcome these obstacles, there has been a burgeoning investigation into the luminescent and photophysical properties of COFs. This review will highlight methods used to fabricate luminescent COFs and discuss the factors that are critical for their production. A collection of known luminescent COF systems will be featured. In addition, the ability to utilize the photophysical properties of COFs for applications related to photocatalysis, solid-state light emitters, and chemical sensing will be addressed. An outlook will address the current progress and remaining challenges facing the field to ultimately expand the scope of their applications.

Insight into volatile iodine uptake properties of covalent organic frameworks with different conjugated structures

The effective capture and storage of volatile radionuclide iodine from the nuclear waste stream is of great significance for environment remediation. Here we synthetize two types of two-dimensional (2D) covalent organic frameworks (COFs) for iodine vapor uptake, including COF-LZU1 with a whole π-π conjugated structure and TpPa-1 with a combination of π-π and p-π conjugated structure. The capacities for iodine vapor uptake are acquired for COF-LZU1 (530 wt%) and TpPa-1 (245 wt%). Thorough studies reveal that the large and intact π-π conjugated system formed by phenyl rings and imine (−CN−) linkers in COF-LZU1 provides materials with ultrahigh iodine vapor uptake by inducing the charge-transfer interactions to transform adsorbed iodine molecules into polyiodide anions. However, the combined π-conjugated structure in TpPa-1 shows no obvious effect on iodine adsorption enhancement. Hence, this study can provide a guidance for the design and construction of ultrahigh-capacity iodine adsorbents.

Postsynthetic functionalization of covalent organic frameworks.

Covalent organic frameworks (COFs) have been at the forefront of porous-material research in recent years. With predictable structural compositions and controllable functionalities, the structures and properties of COFs could be controlled to achieve targeted materials. On the other hand, the predesigned structure of COFs allows fruitful postsynthetic modifications to introduce new properties and functions. In this review, the postsynthetic functionalizations of COFs are discussed and their impacts towards structural qualities and performances are comparatively elaborated on. The functionalization involves the formation of specific interactions (covalent or coordination/ionic bonds) and chemical reactions (oxidation/reduction reaction) with pendant groups, skeleton and reactive linkages of COFs. The chemical stability and performance of COFs including catalytic activity, storage, sorption and opto-electronic properties might be enhanced by specific postsynthetic functionalization. The generality of these strategies in terms of chemical reactions and the range of suitable COFs places them as a pivotal role for the development of COF-based smart materials.

From Highly Crystalline to Outer Surface-Functionalized Covalent Organic Frameworks--A Modulation Approach.

Crystallinity and porosity are of central importance for many properties of covalent organic frameworks (COFs), including adsorption, diffusion, and electronic transport. We have developed a new method for strongly enhancing both aspects through the introduction of a modulating agent in the synthesis. This modulator competes with one of the building blocks during the solvothermal COF growth, resulting in highly crystalline frameworks with greatly increased domain sizes reaching several hundreds of nanometers. The obtained materials feature fully accessible pores with an internal surface area of over 2000 m2 g–1. Compositional analysis via NMR spectroscopy revealed that the COF-5 structure can form over a wide range of boronic acid-to-catechol ratios, thus producing frameworks with compositions ranging from highly boronic acid-deficient to networks with catechol voids. Visualization of an −SH-functionalized modulating agent via iridium staining revealed that the COF domains are terminated by the modulator. Using functionalized modulators, this synthetic approach thus also provides a new and facile method for the external surface functionalization of COF domains, providing accessible sites for post-synthetic modification reactions. We demonstrate the feasibility of this concept by covalently attaching fluorescent dyes and hydrophilic polymers to the COF surface. We anticipate that the realization of highly crystalline COFs with the option of additional surface functionality will render the modulation concept beneficial for a range of applications, including gas separations, catalysis, and optoelectronics.