Friedel-Crafts Research Articles

Introducing the sulfone group as a cellulose-binding site to improve the hydrolysis performance of the solid acid

To clarify the role of the specific sulfur-containing functional groups of solid acids in the hydrolysis of cellulose, it is necessary to prepare a solid acid bearing relatively single sulfur-containing functional groups apart from the –SO3H group. However, diphenylsulfone cannot be polymerized through Friedel-Crafts alkylation, limiting the possibility of preparing sulfone-based solid acids. Therefore, diphenyl sulfide was crosslinked through Friedel-Crafts alkylation, followed by sulfonation and oxidation. The results showed that the sulfone group was successfully introduced onto the solid acid, and the density of –SO3H groups increased by 80.88 % through this strategy. The sulfone group is a strong adsorption site for cellulose, and its introduction leads to a decrease in apparent activation energy. Cellulose conversion and glucose selectivity are as high as 77.54 % and 97.13 %, respectively. Unexpectedly, the stability of the functional groups and carbon skeleton is significantly improved due to the conjugation effect of the sulfone group.

Cover Feature: HFIP‐Mediated Desulfinative Friedel–Crafts Cyclobutenylation Reaction (Chem. Eur. J. 41/2024)

Cover Feature: HFIP‐Mediated Desulfinative Friedel–Crafts Cyclobutenylation Reaction (Chem. Eur. J. 41/2024)

Self-catalytic photochemical three-component reaction for the synthesis of multifunctional 3,3-disubstituted oxindoles

A visible-light-induced, self-catalyzed multi-component reaction has been established, delivering a facile and atom-economic method to 3,3-disubstituted oxindoles with wild functional group tolerance and good to excellent yields under photocatalyst-, oxidant- and base-free conditions. The process involves photocatalytic Friedel–Crafts type coupling, halogenation, and oxidation reactions, which makes it practical and attractive. Moreover, this strategy contributes to the development of an efficient protocol for accessing electrochemically active 3,3-disubstituted oxindoles, which have potential applications in flow batteries.

Synthesis of bilaterally thiadiazole substituted vic-dioxime ligands and investigation of their polymeric metal complexes

In this study, three novels substituted 1,3,4-thiadiazole-derived vic-dioxime ligands and their corresponding polymeric transition metal (Co2+and Ni2+) complexes were synthesized and their structural characterizations were performed. For this purpose, 4,4′-bis(chloroacetyldiphenyl) ether (OKS1) was obtained from the reaction of diphenyl ether with chloroacetyl chloride at a 1:2 molar ratio with the help of the Friedel-Crafts reaction. Our first starting oxime compound “2,2′-(oxybis(4,1-phenylene))bis(N‑hydroxy-2-oxoacetimidoyl) chloride (OKS2)” was obtained from the reaction of OKS1 with butyl nitrite at a 1:2 molar ratio under the catalysis of HCl gas. Then, our final starting vic-dioxime compound “2,2′-(oxybis(4,1-phenylene))bis(N‑hydroxy-2-(hydroxyimino) acetimidoyl) chloride (OKS3)” was obtained from the reaction of OKS2 with hydroxylamine hydrochloride in ethanol media at 40 °C. Then, our three original target vic-dioxime compounds (OKL1-OKL3) were synthesized from the reaction of substituted 2-amino-1,3,4-thiadiazole compounds with OKS3. Structural characterizations of all synthesized organic compounds were made using elemental analysis, FTIR, 1H and 13C NMR and mass spectroscopy methods. Target complexes were obtained from the reaction of all ligands with MCl2.nH2O (M: Co2+and Ni2+) salts, and their structures were elucidated using FTIR, magnetic susceptibility, thermogravimetric analysis, elemental analysis, and ICP-OES spectroscopy methods.

Synthesis and Properties of Cyclic π-Conjugated Molecules and Their Dication and Monoradical Cation.

We synthesized cyclic π-conjugated molecules by double Friedel-Crafts reaction of amino group-substituted 1,2-bis(2-phenylethynyl)benzene with Meldrum's acid derivative. The structures of the cyclic π-conjugated molecules were determined by single-crystal X-ray structure analysis. The oxidation of the dimethylamino group-substituted π-conjugated molecule with NOBF4 gave a closed-shell dication that is stable at >210 °C. The monoradical cation of the di(4-methoxyphenyl)amino group-substituted π-conjugated molecule is stable in dichloromethane solution (half-life of nearly 15 days) and shows near-infrared absorption.

Amino-modified microporous hyper-crosslinked resins for heavy metal ions adsorption

In this work, a high surface area micro/mesoporous hyper-crosslinked resin based on vinylbenzyl chloride and divinylbenzene is synthesized through a solvent-free polymerization followed by Friedel-Crafts alkylation. The hyper-crosslinked resin is then functionalized with amino moieties and the effect of the functionalization on the adsorption of metal ions is evaluated. After a chemical-physical characterization of the hyper-crosslinked resins, equilibrium adsorption tests of Pb(II) and Cu(II) in water are performed. The plain and amino-modified hyper-crosslinked resins (HCLR and HCLR-NH2) exhibit specific surface area (SSA) of about 1800 m2/g and 800 m2/g, respectively. They both exhibit micro/mesoporous structure, and their pore size distribution is modified upon functionalization. The amino-functionalization, while reducing prevalently the mesoporosity of the resin, does not significantly affect the micropores. HCLR-NH2 displays higher efficiency in removing both metal ions from aqueous solution compared to the unmodified resin. HCLR-NH2 is able to capture up to about 70 % of Pb(II) and up to about 48 % of Cu(II) dissolved in water at 5 mg/L concentration while in the same tests, HCLR captures about 25 % of Pb(II) and 17 % of Cu(II). The resins adsorption mechanisms follow the Langmuir model, suggesting a specific and functional groups-related adsorption mechanism. Therefore, the major adsorption capacity of HCLR-NH2 is to be primary attributed to the grafted amino moieties, which establish chelating interactions with the metal cations. Overall, results assess the relevance of the micropores and the amino functionalization to capture Pb and Cu ions via adsorption.

Synthesis of metal-free benzimidazole-based catalysts and its application in CO2 cycloaddition.

Ionic polymers functionalized with hydroxyl, carboxyl, and amino groups can enhance the catalytic activity of catalysts. However, the straightforward preparation of bifunctional ionic polymers containing abundant ionic active sites and hydrogen bond donors remains challenging. In this study, a series of porous ionic polymers (BZIs) containing different hydrogen bond donors (-NH2, -OH, -COOH) were prepared through a simple one-pot Friedel-Crafts alkylation using benzimidazole derivatives and benzyl bromide. The structures and properties of BZIs were characterized by various techniques such as Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, solid-state nuclear magnetic resonance, and scanning electron microscopy. Among the prepared catalysts (BZI-NH2, BZI-OH, and BZI-COOH), BZI-NH2 exhibited the highest catalytic activity and recyclability, achieving a yield of 97% in the CO2 cycloaddition. The synergistic effect of Br-, hydrogen bond donors (-NH-, -NH2), and N+ in BZI-NH2 was found to contribute to its superior catalytic performance. DFT calculations were employed to study the effect of hydrogen bonds, Br-, and N+ in BZI-NH2 and BZI-OH on the CO2 cycloaddition. Using BZI-NH2 as an example, a mechanism was proposed for the synergistic effect between amino groups and bromide ions in catalyzing the CO2 cycloaddition reaction.

Friedel Crafts Reactions Revisited: Some Applications in Heterogeneous Catalysis#

Abstract: Important organic reactions require the use of catalysts. The Friedel-Crafts reactions were discovered by Charles Friedel and James Mason Crafts in 1887. They are an essential catalytic process since they are widely applied in different areas such as fuels, cleaning, and pharmacological products. The reaction is usually carried out in the presence of Lewis acids or Brønsted acids in a homogeneous medium, with the nucleophilic aromatic substrate in excess. Although there is still work in the literature on the Friedel- Crafts reaction in a homogeneous medium using metal halides, the tendency is to replace these catalysts, which generate effluents that are harmful to the environment. Heterogeneous catalysts using solid acids show advantages over homogeneous catalysts, especially concerning separating products from the reaction medium, recycling, and reusing. This paper presents a mini-review focusing on the use of solid acids in Friedel-Crafts reactions.

Effective Removal of Malachite Green Dye from Water Using Low-Cost Porous Organic Polymers: Adsorption Kinetics, Isotherms, and Reusability Studies

In this study, triphenylaniline-based porous organic polymers (TPA-POPs) were successfully prepared by the Friedel–Crafts reaction and applied to adsorb malachite green (MG) dye from water. The TPA-POP was characterized using TEM, SEM, FTIR, 13C (CP/MAS) NMR, BET surface area, and XRD analysis. The results exhibited that the TPA-POP has a high surface area (1625.14 m2/g) with pore volume (0.353 cm3/g) and pore radius (1.57 nm) that reflect the high quantity of MG adsorbed on the TPA-POP. The polymer was evaluated as an excellent adsorbent for MG adsorption from water using the batch method. MG dye removal was optimized as 99.60% (at pH: 6.0, adsorbent dosage (m): 0.01 g, temperature (T): 45 °C, and contact time (t): 300 min). The kinetic data follow the Elovich model, while the isotherm data fit the Langmuir model well with uptake capacity (755.72 mg/g) at T: 45 °C. According to thermodynamic parameters, the adsorption process was endothermic and spontaneous. The adsorption of MG on the TPA-POP occurred via different mechanisms (π–π interaction, electrostatic attraction, and hydrogen bonding). Reusability experiments exhibited that the TPA-POP still maintained high removal efficiency (82.12%) after five cycles. In conclusion, the TPA-POP is a promising adsorbent owing to its cost-effectiveness, high adsorption capacity, high surface area, excellent reusability, and efficient MG removal from aqueous media.

Site-Selective Zn-Metalation in Poly-Triphenyl Amine-based Porous Organic Polymer for Solid-Gas Phase CO2 Photoreduction.

Harvesting solar energy to produce value-added chemicals from carbon dioxide (CO2) presents a promising route for addressing the complexities of sustainable energy systems and environmental issues. In this context, the development of metal-coordinated porous organic polymers (POPs) offers a vital avenue for improving the photocatalytic performance of organic motifs. The current study presents a metal-integrated photocatalytic system (namely, Zn@BP-POP) developed via a one-pot Friedel-Crafts (F.C.) acylation strategy, for solid-gas phase photochemical CO2 reduction to CO (CO2RR). The postsynthetic incorporation of metal (Zn) active sites on the host polymeric backbone of BP-POP significantly influences the catalytic activity. Notably, Zn@BP-POP demonstrates good photocatalytic performance in the absence of any cocatalyst and photosensitizer yielding CO while impeding the competitive hydrogen evolution reaction (HER) from water. The experimental findings collectively propose that the observed catalytic activity and selectivity arise from the synergistic interplay between the singular zinc catalytic centers and the light-harvesting capacity of the highly conjugated polymeric backbone. Further, X-ray absorption spectroscopy (XAS) analysis has significantly highlighted the prominent role played by the ZnN2O4 single sites in the polymeric framework for activating the gaseous CO2 molecules. Further, time-dependent density functional theory (DFT) analysis also reveals the thermodynamic feasibility of CO2RR over HER under optimized reaction conditions. This work cumulatively presents an effective strategy to demonstrate the importance of metal-active sites and effectively establish their structure-activity relationship during photocatalysis.

Microwave-enhanced preparation of finned-FER zeolites and their application in the skeletal isomerization of FAME

The skeletal isomerization of fatty acid methyl esters (FAME) is vital for producing branched-chain esters and is a great tool to improve the cold flow properties of biodiesel. Ferrierite (H-FER) zeolite is an effective catalyst for facilitating this reaction; however, its efficiency can be limited by site accessibility and pore structure. Thus, our research developed a novel method for producing finned-FER zeolites by a seed-mediated approach that applies microwave heating with H-FER as seeds. The main focus was to examine how varying synthesis conditions, particularly microwave heating time, influenced the physical and chemical properties of the produced zeolites; we showed that the optimized condition was achieved with 6 h of microwave heating, revealing well-defined finned crystals and improved characteristics. Finally, the study evaluated the catalytic performance of these finned-FER zeolites. The Friedel-Crafts alkylation reaction, serving as a model reaction, was employed to assess the performance of the materials. We also accessed the performance of these materials in the same reaction in the presence of triphenylphosphine, offering a deeper understanding of the real active sites and their accessibility. Furthermore, the isomerization reactions of methyl oleate were explored to evaluate the practical applicability of the synthesized zeolites. The results revealed that branched isomers exceeding 70 % yield were achieved at 89 % conversion for the best catalyst at a temperature of 250 °C and 20 bar of H2 for 6 h. Thus, this research proposes a more efficient method for synthesizing finned-FER zeolites and systematically analyzes their characteristics, highlighting potential improvements in catalytic efficiency and sustainability.

A Thiophene Functionalized Hf(IV)-Organic Framework for the Detection of Anti-Neoplastic Drug Flutamide and Biomolecule Hemin and Catalysis of Friedel-Crafts Alkylation.

Development, rapid detection and quantification of anticancer drugs in biological samples are crucial for effective drug monitoring. The present work describes the design of a Hf(IV)-based metal-organic framework (MOF) (1) by the reaction between Hf(IV) ion and 2-(thiophene-2-carboxamido)terephthalic acid linker with the surface area of 571 m2 g-1. Desolvated MOF (1') displayed highly discriminative fluorescence sensing properties for the antineoplastic drug flutamide and biomolecule hemin in an aqueous medium in the presence of co-existing biomolecules and ions. The MOF's response time for sensing flutamide and hemin was less than 5 s with low detection limits of 1.5 and 0.08 nM, respectively. Additionally, 1' also demonstrated recyclability up to five cycles and maintained its sensing ability across different pH media, various water samples, and biological fluids. Experimental and theoretical analyses suggested photoinduced electron transfer and inner-filter effect in the presence of flutamide and Förster resonance energy transfer in the presence of hemin are most likely reasons behind the fluorescence quenching of MOF. Furthermore, the MOF demonstrated catalytic activity in Friedel-Crafts alkylation reactions, providing a 96 % yield with slight decay in its activity over four uses. The enhanced activity of 1' compared to Hf-BDC and Hf-BDC-NH2 (BDC: 1,4-benzenedicarboxylic acid) is due to the functionalized thiophene moieties through hydrogen bond donating sites, confirmed by a series of control experiments.

Selective Capturing of the CO2 Emissions Utilizing Ecological (3-Mercaptopropyl)trimethoxysilane-Coated Porous Organic Polymers in Composite Materials.

Capturing carbon dioxide (CO2) is still a major obstacle in the fight against climate change and the reduction of greenhouse gas emissions. To address this problem, we employed a simple Friedel-Crafts alkylation to investigate the effectiveness of porous organic polymers (POPs) based on triphenylamine (TPA) and trihydroxy aryl terms derived from chloranil (CH), designated as TPA-CH POP. We then treated the TPA-CH POP with (3-mercaptopropyl)trimethoxysilane (3-MPTS), forming a TPA-CH POP-SH nanocomposite to enhance CO2 capture. Utilizing FTIR, solid-state NMR, SEM, TEM, along with XPS techniques, the molecular makeup, morphological characteristics, as well as physical features of TPA-CH POP and the TPA-CH POP-SH nanocomposite were thoroughly explored. Upon scorching to 800 °C, the TPA-CH POP-SH nanocomposite demonstrated more thermal durability over TPA-CH POP, achieving a char yield of up to 71.5 wt.%. The TPA-CH POP-SH nanocomposite displayed a 2.5-times better CO2 capture, as well as a comparable adsorption capacity of 48.07 cm3 g-1 at 273 K. Additionally, we found that the TPA-CH POP-SH nanocomposite exhibited an improved CO2/nitrogen (N2) selectivity versus the original TPA-CH POP. Typical enthalpy changes for CO2 capture were somewhat increased by the 3-MPTS coating, indicating greater binding energies between CO2 molecules and the adsorbent surface. Our outcomes demonstrate that a TPA-CH POP composite coated with MPTS is a viable candidate for effective CO2 capture uses. Our findings encourage the investigation of different functional groups and optimization strategies.

Novel centratherin derivatives: Molecular docking design, asymmetric synthesis, and antitumoral activity

Centratherin is a sesquiterpene lactone that has the potential to inhibit target proteins for cancer therapy, such as the inflammatory mediator NF-κB. Indoles also exhibit antitumoral activity and can modulate the NF-κB signaling pathway. Here we describe a molecular-docking guided semi-synthesis of indole-containing centratherin derivatives. In silico studies indicated that these compounds have high affinity to NF-κB and do not present toxicity or carcinogenicity. Two enantiomeric series of indole-centratherin hybrids were synthesized in three steps with good yields and ee, employing an organocatalyzed Friedel-Crafts alkylation as a key step. The compounds were evaluated against human leukemia K562 cells and showed promising antitumoral activities with IC50 ranging from 0.49 to 7.83 μM.

A ZSM-5 zeolite nanosheet with single-unit-cell thickness templated by bi-ammonium surfactants with large-diameter hydrophobic groups

Ultra-thin zeolite nanosheets have received widespread attention due to their superior catalytic performance compared to bulk zeolites. Here, we have designed a new structure-directing agent with a tert-butyl benzene group as the large-diameter hydrophobic end of a bi-ammonium surfactant molecule. Using this novel structure-directing agent, zeolite nanosheets with a thickness of ∼ 2.5 nm were synthesized, which exhibit better catalytic performance than bulky zeolites in the Friedel-Crafts alkylation reaction of trimethylbenzene and benzyl alcohol.

Hyper-Cross-Linked Resin Modified by a Micropore Polymer for Gas Adsorption and Separation.

Polymerization confined to the pore was first adapted for the nanoscale structure adjustment of adsorption resin. The self-cross-linked polymer (P-1) formed in the pore of hyper-cross-linked resin (HR) by the Friedel-Crafts reaction of p-dichloroxylene (p-DCX), occupying the macropore of the HR resin and bringing about an external micropore. Compared with the raw HR resin, the volume of the micropore of HR@P-1 in 0.4 < D < 1 nm increased but the volume of the macropore has obviously decreased. After the loading of P-1 in the nanopore of HR, HR@P-1 has better gas adsorption performance. At 298 and 100 KPa, the adsorption capacity of CO2 is almost 30% higher than that of HR, reaching 35.7 cm3/g, due to the increase in the smaller micropore volume. Moreover, HR@P-1 has also been found to be the first C2H6-selective adsorption resin. The uptake of C2H6 is up to 56 cm3/g, and the IAST selectivity of C2H6/CH4 reaches 15.3. HR@P-1 can also separate syngas efficiently at ambient temperature and be regenerated by simple vacuum operation.

Production, thermal recycling, and application of cardanol-based polyurethane foam with phenol-carbamate bonds

The economic processing, sustainable recycling, and environmentally friendly application of polyurethane (PU) foams are important issues that need to be addressed urgently. In this study, we propose a strategy for the comprehensive utilization of cardanol and cashew shells to design cardanol-based PU (CPU) foams and wood-plastic films that can be recycled and reused. Firstly, cardanol-based polyphenols (CBPs) with a phenolic hydroxyl content of 3.29 mmol/g were prepared by Friedel-Crafts alkylation reaction using cardanol and guaiacol as raw materials. Subsequently, CPU foams were prepared by reacting CBPs with isocyanate, and the vertical and parallel compressive strengths could reach up to 0.27 MPa and 0.32 MPa, respectively, when the addition of CBPs was 80 %. These CPU foams, containing dynamic phenol-carbamate bonds, could be hot-pressed into transparent and smooth CPU films with tensile strengths of up to 30.5 MPa and could be re-formed at least three times. Finally, CPU foam and cashew shell waste were mixed and hot-pressed to produce a green wood-plastic composite with a tensile strength of up to 38.8 MPa. The resulting CPU-Wood films could be repaired or reshaped at least five times (38.0 MPa and 38.1 MPa) and could be formed into various shapes. This research paves the way for large-scale industrial production of recyclable and regenerative bio-based foams, making effective use of waste materials to achieve environmentally friendly production processes.

Porous organic polymers from cashew nut shell liquid: Derived carbonized material for carbon dioxide capture

AbstractThe fast developing world is in search of measures to control the accumulation of unused by‐products and waste materials generated during the production of useful commodities. Accordingly, wastes from agro‐industrial sectors can form raw materials for the production of various resources that are extensively used in many areas such as gas sorption and energy production. In the present work, cashew nut shell liquid (CNSL), the vesicant liquid present in the outer shell of cashew seed, forms the source material for the synthesis of porous organic polymers for carbon dioxide capture. Herein, novel types of hypercrosslinked polymers (HCPs) are synthesized via a simple Friedel–Crafts reaction with CNSL as the starting material. Polymerization of natural CNSL with dimethoxymethane/bis‐(chloromethyl)‐biphenyl as external crosslinker provides products in quantitative yield. One of the synthesized HCP is tuned to attain the required high porosity by carbonization at elevated temperatures using an activator. Thus, activated carbon material prepared at 700°C is found to have a high surface area of 880 m2/g with a good carbon dioxide adsorption capacity of 14.72 wt%. These porous materials had moderate isosteric heat of adsorption (23–31 kJ/mol) with excellent recycling capability.

Metal‐ and Acid‐Free Photocatalytic Approach Using Quinone‐Based Hyper‐Crosslinked Porous Catalysts for the Valorization of Glycerol into Solketal

Two metal‐ and acid‐free anthracene (AN) and anthraquinone (AQ)‐based photocatalysts (HCP‐AQ‐2Ph and HCP‐AN‐2Ph) are synthesized and used for the effective acetalization of glycerol to obtain selectively solketal, an added‐value compound with several industrial applications and high demand as an oxygenated additive of fuels. HCP‐AQ‐2Ph and HCP‐AN‐2Ph are prepared by a Friedel–Crafts coupling reaction between the AQ or AN and biphenyl (2Ph) as comonomer which leads to the formation of high thermally stable hyper‐crosslinked porous networks with specific surface areas of 295 and 596 m2 g−1, respectively. Initial tests suggest that HCP‐AN‐2Ph is a less efficient catalyst compared to HCP‐AQ‐2Ph. However, subsequent runs indicate that during the first trial, the AN units are oxidized, resulting in a catalyst (HCP‐AN(OX)‐2Ph) just as effective as the AQ‐based one. The quantitative and selective conversion of glycerol into solketal is achieved in just 3 h using a 4 wt% catalyst and maintaining this catalytic performance for at least 5 cycles. In addition, the process can be scaled allowing the obtaining of solketal with high purity on a gram scale. These results place these catalysts among the most effective for the selective production of solketal from glycerol compared to previously reported metal‐ or acid‐catalyzed reaction.

Recent advances in research on sample pretreatment methods based on supramolecular-derived porous organic polymers

Porous organic polymers (POPs) are a class of materials composed of organic building blocks usually consisting of the elements C, H, O, N, and B and other light elements connected by covalent bonds. Owing to the diversity of synthesis methods in organic chemistry, POPs can be prepared by Suzuki coupling, Sonogashira-Hagihara cross-coupling, Schiff-base condensation, Knoevenagel condensation, and Friedel-Crafts alkylation. POPs show great application potential in the field of sample pretreatment because of their large specific surface area, adjustable pore size, high tailorability, and easy modification. The design of new functional building blocks is an important factor in advancing the development of POPs and is key to the efficient separation and enrichment of target molecules in complex substrates. In recent years, supramolecular-derived compounds have provided new inspiration and breakthroughs in the construction of POPs on account of their excellent host-guest recognition properties, simple functionalization strategies, and adjustable topological configurations. The "cavitand-to-framework" approach, that is, the knitting of 0D macrocycles into hierarchical 2D or 3D POPs using suitable linkers, and extension of the research scope of supramolecular chemistry from discrete cavities to rigidly layered porous organic frameworks can lead to significant improvements in the porosity and stability of supramolecular-derived compounds. They can also provide an effective means to expand the structural diversity of POPs and generate layered structures with high porosity. This review summarizes the preparation strategies and structural characteristics of supramolecular-derived POPs with different structures, such as crown ether-based POPs, cyclodextrin-based POPs, and calixarene-based POPs. The promising applications of these materials in sample pretreatment focusing on food analysis and environmental monitoring, including epoxides, organic dyes, heavy metals, algatoxins, halogens, and antibiotic drugs, are then summarized. Next, the extraction mechanisms mainly attributed to host-guest recognition, π-π stacking, and hydrogen-bonding and electrostatic interactions between the supramolecular structures and analytes are described. The key role and potential advantages of the different preparation strategies and structural characteristics of these POPs in sample pretreatment are also discussed. Finally, the future prospects and remaining challenges of supramolecular-derived POPs are proposed. Supramolecular-derived POPs can not only achieve the rapid and selective extraction of target analytes during sample pretreatment but also improve the extraction effect of online solid phase extraction technologies. However, although numerous supramolecular-derived POPs have been developed, few have been applied in the field of sample pretreatment. Thus, the expansion of the application potential of more POP materials requires further exploration and research. The design and synthesis of supramolecular-derived POPs with highly selective recognition performance remains an important research direction in the field of sample pretreatment.