Sonogashira-Hagihara Coupling Reaction Research Articles

Conjugated microporous polymer for solid-phase extraction of neonicotinoid insecticides from environmental water samples

Conjugated microporous polymers (CMPs) have unique characteristics and have been used in a range of fascinating applications in separation sciences. In this study, a CMP, designated as CMP-1, was synthesized via the Sonogashira-Hagihara coupling reaction using 1,3,5-triphenylbenzene and 1,4-dibromobenzene as building blocks. CMP-1 features a large surface area, abundant micropore structures, and excellent stability, making it a promising solid-phase extraction adsorbent for the efficient enrichment of neonicotinoid insecticides (NEOs). Under the optimized conditions, CMP-1 was combined with high-performance liquid chromatography and diode array detection to enable the detection of NEOs with a wide linear range (0.5–200 μg·L–1), a low detection limit (0.26–0.58 μg·L–1), and acceptable precision. The developed method was applied to determine spiked NEOs in three types of environmental water samples, with recoveries of 73.7%–112.0% and relative standard deviations of 0.6%–9.4%.

Electrochemical chiral sensor for recognition of amino acid enantiomers with cyclodextrin-based microporous organic networks

BackgroundChirality is a ubiquitous phenomenon in nature, but enantiomers exhibit different pharmacological activities and toxicological effects. Therefore, Chiral recognition plays a pivotal role in various fields such as life sciences, chemical synthesis, drug development, and materials science. The synthesis of novel chiral composites with well-defined loading capabilities and ordered structures holds significant potential for electrochemical chiral recognition applications. However, the design of selective and stable electrochemical chiral recognition materials remains a challenging task. ResultIn this work, we construct a simple and rapid electrochemical sensing platform for tryptophan (Trp) enantiomer recognition using cyclodextrin-modified microporous organic network as chiral recognition agent. CD-MON with chiral microenvironment was prepared by Sonogashira-Hagihara coupling reaction of the chiral molecule heptyl-6-iodo-6-deoxyβ-cyclodextrin and 1, 4-Diethynylbenzene. The adhesion of BSA makes CD-MON firmly fixed on the electrode surface, and as a chiral protein, it can improve the chiral recognition ability through synergistic effect. Chiral amino acids are in full contact with the chiral microenvironment during pore conduction of MON, and L-Trp is more stably bound to CD-MON/BSA due to steric hindrance, host-guest recognition and hydrogen bonding. Therefore, the electrochemical sensor can effectively identify tryptophan enantiomers (IL-Trp/ID-Trp = 2.02), and it exhibits a detection limit of 2.6 μM for L-Trp. UV–Vis spectroscopy confirmed the adsorption capacity of CD-MON towards tryptophan enantiomers in agreement with electrochemistry results. SignificanceThe prepared chiral sensor has excellent stability, reproducibility (RSD = 3.7%) and selectivity, realizes the quantitative detection of single isomer in tryptophan racemic and quantitative analysis in real samples with 94.0%–101.0% recovery. This work represents the first application of MON in chiral electrochemistry which expands the application scope of chiral sensors and holds great significance in separation science and electrochemical sensing.

Construction of Conjugated Organic Polymers for Efficient Photocatalytic Hydrogen Peroxide Generation with Adequate Utilization of Water Oxidation.

The visible-light-driven photocatalytic production of hydrogen peroxide (H2O2) is currently an emerging approach for transforming solar energy into chemical energy. In general, the photocatalytic process for producing H2O2 includes two pathways: the water oxidation reaction (WOR) and the oxygen reduction reaction (ORR). However, the utilization efficiency of ORR surpasses that of WOR, leading to a discrepancy with the low oxygen levels in natural water and thereby impeding their practical application. Herein, we report a novel donor-bridge-acceptor (D-B-A) organic polymer conjugated by the Sonogashira-Hagihara coupling reaction with tetraphenylethene (TPE) units as the electron donors, acetylene (A) as the connectors and pyrene (P) moieties as the electron acceptors. Notably, the resulting TPE-A-P exhibits a remarkable solar-to-chemical conversion of 1.65% and a high BET-specific surface area (1132 m2·g-1). Furthermore, even under anaerobic conditions, it demonstrates an impressive H2O2 photosynthetic efficiency of 1770 μmol g-1 h-1, exceeding the vast majority of previously reported photosynthetic systems of H2O2. The outstanding performance is attributed to the effective separation of electrons and holes, along with the presence of sufficient reaction sites facilitated by the incorporation of alkynyl electronic bridges. This protocol presents a successful method for generating H2O2 via a water oxidation reaction, signifying a significant advancement towards practical applications in the natural environment.

Carbon derived from orange peel waste for preparation of benign bimetallic catalyst in organic reactions

In this work, a convenient approach has been applied to discover the potential valorization of biomass waste such as orange peel in which PdCu-based nanostructured systems were synthesized via a one-step in-situ dry-milling approach to obtain the benign bimetallic catalysts with different palladium(Pd) and Copper(Cu) loadings on the orange peel support (Pd1%Cu1%, Pd0.3%Cu0.7%, Pd0.5%Cu0.5%, Pd0.5%Cu1%). Catalytic applications of these new composites were investigated in the Sonogashira-Hagihara coupling reaction as well as the Sonogashira–click reaction sequence to the preparation of substituted 4-aryl-1,2,3-triazoles and reduction of nitroaromatics under mild reaction conditions. Catalytic tests with the four activated carbons catalysts showed that the C@Pd1%Cu1% catalyst was the most active in the Sonogashira-Hagihara coupling reaction compared to the other catalysts. Also, the C@Pd0.5%Cu0.5% catalyst showed the highest catalytic activity in the reduction of 1-chloro-4-nitrobenzene and 4-nitrophenol in comparison with other prepared carbon catalysts.

Porphyrin-Based Conjugated Microporous Polymer Loaded with Nanoscale Zerovalent Iron for the Degradation of Organic Pollutants under Visible Light.

The degradation of organic dye from waterbodies is of great significance for clean production and environmental remediation. Herein, two porphyrin-based conjugated microporous polymers (CMPs) loaded with nanoscale zerovalent iron (named as Por-CMPs-1-2@nZVI) were successfully fabricated by Sonogashira-Hagihara coupling reactions and the liquid-phase method. The as-synthesized Por-CMPs-1-2@nZVI composites were characterized by various means of analysis, and it was confirmed that Por-CMPs-1-2 loaded with nZVI had good photocatalytic performance. Calculated by ultraviolet-visible spectrum, the band-gap energies of Por-CMPs-1@nZVI and Por-CMPs-2@nZVI were 1.45 and 1.32 eV, respectively, indicating that both can be activated by visible light. The photodegradation of organic dye experiments demonstrated that Por-CMPs-2@nZVI degraded 98.0% of 10 ppm Methylene Blue (MB) within 150 min, which is higher than that of Por-CMPs-1-2 and Por-CMPs-1@nZVI. The experiment of active substance capture and mechanism of ESR confirmed that superoxide anion and hydroxyl radical were the primary valid substances in the photodegradation process of MB. In addition, the preparation of membrane materials was shown to be a successful strategy to realize engineered scale-up production.

A hexaazatriphenylene‐based porous organic polymer for high performance supercapacitor

AbstractPorous organic polymers (POPs) with high physiochemical stability and pseudocapacitive activity are crucial for supercapacitors with high specific capacitance and long cycle life. We report herein a hexaazatrinaphthylene‐based POP (HPOP‐1) for high‐performance supercapacitor by introducing redox‐active hexaazatrinaphthylene (HATN) moiety through Sonogashira–Hagihara coupling reaction. HATN moiety can undergo a proton‐induced electron transfer redox reaction, which endows HPOP‐1 with high pseudocapacitive activity. As electrode materials for supercapacitor application, HPOP‐1 exhibits high specific capacitance (667 F g−1 at 0.5 A g−1) and long‐term cyclic stability (90% capacitance retention after 10,000 cycles at 5 A g−1) in a three‐electrode system with 1 M H2SO4 as the electrolyte. In addition, HPOP‐1 also exhibits a specific capacitance of 376 F g−1 at 0.5 A g−1 in 1 M KOH electrolyte. An asymmetric supercapacitor was further fabricated with HPOP‐1 as negative electrode and rGO as positive electrode, respectively. The device delivers a specific capacitance of 63 F g−1 at 0.5 A g−1 and a rate performance of 37 F g−1 at 5 A g−1. Our work provides a facile approach for the design and preparation of pseudocapacitive POPs with high specific capacitance and long cycle life.

Removal of PM and oil mist from automobile exhaust by a “hamburger” structured conjugated microporous polymers membrane

The purification treatment of automobile exhaust has attracted great attention because of the severe harm of automobile exhaust to the global environment and human health. Herein, inspired by capillarity, we adopted a very simple face-to-face constrained growth method to prepare a conjugated microporous polymers membrane (C-CMPs-M) with a “Hamburger” structure through Sonogashira-Hagihara (S-H) coupling reaction for purification and filtration of gaseous, solid and liquid pollutants in automobile exhaust. Thanks to such a special structure, the C-CMPs-M−1 membrane shows an extremely high efficiency of capture and interception of PM2.5 and PM10 (greater than99.5 %) and PM0.3 (greater than95%) in the exhaust gas obtained at different engine speeds. Unlike those hydrophilic filtration materials which suffer the drawback of less tolerance in high humidity conditions, the unique superhydrophobic chemistry of the CMPs membrane makes it possible to efficiently intercept PM under high humidity conditions, and the filtration efficiency basically remains unchanged within 10 h. More interestingly, the super lipophilicity of the membrane endows it excellent oil absorption performance, e.g., high absorption of 907.61 % of its own weight for engine oil was detected and consequently good oil retention performance was also obtained. It also has a strong absorption performance for the unburned oil mist ejected from the exhaust. Based on its ideal porous structure, high interception efficiency, and good physicochemical stability at high humidity and high temperatures conditions, therefore, our C-CMPs-M−1 shows great potential in automobile exhaust purification applications.

Bimetallic AuNi nanoparticles supported on mesoporous MgO as catalyst for Sonogashira-Hagihara cross-coupling reaction

Gold catalysts have been reported to be applied only for the Sonogashira-Hagihara reaction of iodobenzene and phenylacetylene under harsh reaction conditions, while the scope of the reaction has not been expanded for coupling reaction of other aryl halides and alkynes. In this investigation, a cost-effective, Pd-free catalyst based on mesoporous magnesium oxide supported bimetallic AuNi nanoparticles (m-MgO@AuNi) have been synthesized by hydrothermal method and its efficiency has been demonstrated in Sonogashira-Hagihara cross-coupling reaction. The m-MgO@AuNi nanocatalyst was structurally and morphologically characterized using X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS) and the mesoporous structure of MgO has been confirmed through BET analysis. Using this palladium-free catalyst, Sonogashira-Hagihara coupling reaction of aryl iodides and aryl bromides with alkynes have been successfully performed and catalyst was recycled for several times. The results demonstrate that the synergistic effect between Au, Ni and mesoporous MgO support plays key role in enhancement of m-MgO@AuNi catalytic activity in Sonogashira-Hagihara reaction.

Visible photosensitized sonogashira-hagihara coupling through in situ prepared palladium catalyst in N,N-dimethylformamide under copper and amine-free additives

In this study, copper and amine-free photosensitized Sonogashira-Hagihara coupling reaction using Pd(OAc)2 and p-nitrobenzophenone in N,N-dimethylformamide(DMF) under blue LED irradiation was reported. Effect of benzophenone, p-methoxybenzophenone and p-nitrobenzophenone as photosensitizers in Sonogashira-Hagihara reaction were studied in which higher yields were achieved using p-nitrobenzophenone. In situ preparation of palladium nanoparticles and the effect of p-nitrobenzophenone were confirmed using UV–Vis and dynamic light scattering (DLS).It was proposed that the DMF affected the formation and stabilization of palladium nanoparticles. Using this catalytic system, aryl iodides and bromides were reacted efficiently with alkynes between 25 and 60 °C.

Molecule-guided synthesis of conjugated microporous polymers with imidazole derivative units for efficient capture of volatile iodine

Radioactive iodine as a harmful fission product can be released in the environment and bring unpredictable risks to humans even at trace. Porous organic materials with flexible units and high porosity are potential adsorbents for iodine removal. Herein, four molecule-guided conjugated microporous polymers (ImCMPs) with imidazole derivative units were synthesized by Sonogashira-Hagihara coupling reactions and used for the capture of iodine in vapour and solution. With the permanent nanopores, conjugated networks and N-rich units, ImCMPs all show higher uptakes of volatile iodine than the corresponding monomers which have strong adhesion ability to iodine. Remarkably, the vapour iodine uptake of ImCMP-1 up to 2.36 g g−1 at 80 °C, and ImCMP-1 with privileged imidazolyl unit and highest specific surface area possesses the exceptional potential for encasing iodine. This result provides a persuasive approach for design synthesis of excellent adsorbents.

Low-amount palladium supported on Fe-Cu MOF: Synergetic effect between Pd, Cu and Fe in Sonogashira-Hagihara coupling reaction and reduction of organic dyes

FeCu MOF has been prepared via solvothermal method and the resulting bimetallic MOF was employed for stabilization of Pd species. Obtained Pd(II)@NH2BDC-FeCu MOF could act as an effective environmental catalyst in Sonogashira-Hagihara coupling reaction and the reduction of organic dyes. This recyclable catalyst demonstrated high catalytic activity for Sonogashira reaction of aryl iodides and aryl bromides with alkynes. Rhodamine B and methyl red as organic dyes were instantly reduced. Pd(II)@NH2BDC-FeCu/MOF was characterized by TEM, XPS, FT-IR, BET, XRD, and SEM. In addition, the synthesized catalyst was recyclable and reusable for 6 sequential times without deteriorating remarkable in catalytic performance for reaction of iodobenzene with phenylacetylene.

Perfluorinated conjugated microporous polymer for targeted capture of Ag(I) from contaminated water

The maximum targeted capture silver from contaminated water is urgently necessary for sustainable development. Herein, the perfluorination conjugated microporous polymer adsorbent (F-CMP) has been fabricated by Sonogashira-Hagihara coupling reaction and employed to remove Ag(I) ions. Characterizations of NMR, XPS and FT-IR indicate the successful synthesis of F-CMP adsorbent. The influence factors of F-CMP on Ag(I) adsorption behavior are studied, and the adsorption capacity of Ag(I) reaches 251.3 mg/g. The experimental results of isothermal adsorption and kinetic adsorption are consistent with the Freundlich model and pseudo-second-order isothermal adsorption model, which follows a multilayer adsorption behavior on the uniform surface of the adsorbent, and the chemical adsorption becomes the main rate-limiting step. Combined with DFT calculation, the adsorption mechanism of Ag(I) by F-CMP is elucidated. The peaks shift of sp before and after adsorption is larger than that of F1s, suggesting that the –CC– on the F-CMP becomes the dominant chelation site of Ag(I). Furthermore, F-CMP exhibits specific adsorption for Ag(I) in polymetallic complex water, with the maximum selectivity coefficient of 31.5. Our study may provide a new possibility of perfluorinated CMPs for effective capture of Ag(I) ions to address environmental issues.

Zeolitic imidazolate frameworks-67 (ZIF-67) supported PdCu nanoparticles for enhanced catalytic activity in Sonogashira-Hagihara and nitro group reduction under mild conditions

A bimetallic PdCu supported on amine functionalized ZIF-67 is shown to be efficient catalyst in Sonogashira-Hagihara coupling reaction of aryl iodides at room temperature and aryl bromides at 40 ºC. In addition, the catalyst is used in the reduction of 4-nitrophenol (4-NP) at room temperature. The analyses of several experiments are developed in order to demonstrate the existence of synergetic affects between Pd, Cu and Co particles in the named reactions. The stability and reusability of this catalyst are also assessed and its efficiency is compared with other reported catalysts in the same transformations.

Co-Crystal Formation of Partially Fluorinated 1,3,5-Tris(phenylethynyl)benzenes.

Several rigid 1,3,5‐tris(phenylethynyl)benzenes with different fluorination patterns were synthesized through selective Sonogashira‐Hagihara coupling reactions to analyze the packing behavior in solid‐state structures. The aggregation is dominated by various intermolecular interactions between aryl substituents, triple bonds, C−H bonds and H⋅⋅⋅F contacts. Co‐crystallization experiments for the analysis of preferred aryl‐aryl‐interactions led to 1 : 1 complexes. Intermolecular phenyl‐perfluorophenyl interactions with short centroid‐centroid distances are dominating these co‐crystal structures. They lead to melting point increases of up to 49 °C for the co‐crystals compared to the pure substances.

Metal scavenging and catalysis by periodic mesoporous organosilicas with 2,2′‐bipyridine metal chelating ligands

AbstractA periodic mesoporous organosilica containing 2,2′‐bipyridine (BPy‐PMO) was assessed as a metal scavenger and heterogeneous catalyst. The functionalized PMO was synthesized based on a modified version of a previously reported procedure and showed a large surface area with crystal‐like pore walls and uniformly small particles. The small BPy‐PMOs (s‐BPy‐PMOs) exhibited efficient adsorption and removal of palladium (Pd2+) and copper (Cu2+) ions from THF solutions, as confirmed by inductively coupled plasma and UV/vis spectroscopy analyses. The removal efficiencies for Pd and Cu were determined to be 99.9% and 97.5%, respectively. This material was also used to scavenge residual Pd and Cu from reagent solutions following Sonogashira–Hagihara coupling, during which C–C bonds are generated based on catalysis by these metals. Moreover, Pd2+ supporting s‐BPy‐PMO was found to act as an efficient heterogeneous catalyst for the Sonogashira–Hagihara coupling reaction and could be easily separated from the reaction solution by simple filtration and reused.

Porous organic/inorganic polymers based on double-decker silsesquioxane for high-performance energy storage

Two porous organic/inorganic microporous polymers (TPE-DDSQ POIP and Car-DDSQ POIP) were prepared through the Sonogashira-Hagihara coupling reaction of DDSQBr with 1,1,2,2-tetrakis(4-ethynylphenyl)ethene (TPE-T), and 3,3´,6,6´-tetraethynyl-9,9´-bicarbazole (Car-T); respectively. The chemical structure and properties of these two materials including thermal stability, porosity, crystallinity, and morphology were characterized in detail by using various instruments. Based on TGA analyses, Car-DDSQ POIP exhibited high thermal degradation temperature up to 439 °C and char yield up to 77.4 wt.% because inorganic DDSQ unit could enhance the thermal stability as expected. The electrochemical results revealed that TPE-DDSQ POIP and Car-DDSQ POIP showed specific capacitance of 22 and 23 F g−1 at 1 A g−1; respectively in a three-electrode with KOH solution (6 M) as electrolyte and capacitance retention at about 93% after 2000 galvanostatic charge–discharge cycles.

Rational design and synthesis of a task-specific porous organic framework featured azobenzene as a photoresponsive low-energy CO2 adsorbent

An azobenzene-containing porous organic framework (POF) was rationally designed and synthesized via Sonogashira-Hagihara coupling reaction. By virtue of high porous skeleton and azobenzene as light responsive group, this task-specific POF exhibits the reversible stimuli-responsive adsorption property triggered by UV irradiation and heat treatment. The initial Brunauer-Emmet-Teller (BET) surface area of this porous material is 571 ​m2 ​g−1, while the BET surface area after UV irradiation decreases to 550 ​m2 ​g−1 along with the reduction of micropores around 0.5 ​nm and 1.3 ​nm during the trans to cis isomerization process. Furthermore, CO2 sorption isotherms show a slight decrease, which is caused by the trans to cis conversion of azobenzene side group. It is worth mentioning that CO2 uptakes of POFs are almost constant for three cycles via alternating external stimuli to confirm the excellently reversible switchability of trans-to-cis isomerization.

Synthesis of functional conjugated microporous polymer/TiO2 nanocomposites and the mechanism of the photocatalytic degradation of organic pollutants

We successfully synthesize six kinds of functional conjugated microporous polymer (CMP) containing amino, hydroxyl, carboxyl and ester groups by a Sonogashira–Hagihara coupling reaction. These CMPs exhibit type-I nitrogen gas sorption isotherms, and their pore widths are approximately 1.28–1.86 nm with a relatively narrow pore size distribution that is attributed to microporous structures. By blending CMPs with TiO2 under solvothermal conditions, TiO2 is uniformly coated onto the surfaces of the CMPs, and CMP/TiO2 nanocomposites are synthesized successfully. The novel nanocomposites show excellent photocatalytic properties for the degradation of organic pollutants, such as methylene blue, ciprofloxacin and tetracycline, under visible light. The degradation rate of organic pollutants is higher than 96.8%, and after 5 recycling cycles, the degradation efficiency is still more than 93%. The effects of the different functional groups of CMPs on the photocatalytic properties are discussed for the first time. CMP/TiO2 with carboxyl groups show the smallest band gap, highest photocurrent intensity and lowest resistance compared to those of nanocomposites with amino, hydroxyl and ester groups. This result may be caused by the high electronegativity of carboxyl groups, which enhances the charge transfer rate. The photocatalytic mechanism of the CMP/TiO2 nanocomposites is investigated, and the superoxide anion (·O2−) is the main active species in the photocatalytic degradation process.

Synthesis, Photophysical and Electrochemical Properties of 1-, 2-, and 6-(2-Benzofuryl)azulenes

Abstract The synthesis of 2- and 6-(2-benzofuryl)azulenes was accomplished by the Sonogashira-Hagihara coupling reaction of the corresponding haloazulenes with 2-ethynylphenol. 1-(2-Benzofuryl)azulenes were prepared by the decarboxylation of the corresponding 3-methoxycarbonyl derivatives with 100% H3PO4, of which the synthesis has been reported by us, recently. The photophysical properties of the (2-benzofuryl)azulenes were investigated by UV/Vis and fluorescence spectroscopies that revealed their pronounced halochromic behavior and luminescent characteristics under the light-irradiation in acidic media. The electrochemical properties of (2-benzofuryl)azulenes were also evaluated by voltammetry experiments and spectroelectrochemistry measurements.

Photonic Switching Porous Organic Polymers toward Reversible Control of Heterogeneous Photocatalysis.

Sonogashira-Hagihara coupling reaction of photoswitchable dithienylethene (AEDTE) with metal-free 5,10,15,20-tetrakis(4-iodophenyl)porphyrin and its metal derivatives (MTIPP, M = H2, Zn(II), Fe(II)) results in three porous organic polymers (POPs) including AEDTE-H2TIPP-POP, AEDTE-ZnTIPP-POP, and AEDTE-FeTIPP-POP. The morphology, components, and structures of newly obtained POPs have been examined by a range of spectroscopic and microscopic techniques including infrared spectroscopy (IR), solid-state UV-vis diffuse reflectance spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The porous structures have been estimated by nitrogen and carbon dioxide sorption isotherms at 77 and 196 K, respectively. The open-AEDTE-H2TIPP-POP with AEDTE in an open form was revealed to be an effective and stable heterogeneous photocatalyst for visible light-driven oxidation of N-methylpyridinium salts possibly because of its relatively large specific surface area. In particular, a proof-of-concept of photoswitchable POP photocatalysts has been established using different light irradiation upon open-AEDTE-H2TIPP-POP to control its heterogeneous photocatalytic behaviors because of the adjustment over the electron transfer process and porous structures through photoisomerization of AEDTE. The present result highlights the bright perspective of photoswitching POPs in the field of materials chemistry and catalysis community.