Sonogashira-Hagihara Coupling Research Articles

Synthesis of (Z)-Enediynes via Stereoinvertive Nucleophilic Substitution of (E)-Sulfonylethenes with Arylethynide, and Their Aggregation-Induced Optical Properties.

(Z)-Enediynes were successfully synthesized from a trio of terminal ethynes through consecutive three-step reactions: iodosulfonylation of ethyne with I2/PhSO2Na, followed by ethynylations of iodo and sulfonyl moieties of the resulting iodosulfonylethene via Sonogashira-Hagihara coupling and nucleophilic addition-elimination, respectively. The molecular structure of the obtained (Z)-enediyne was fully characterized by X-ray crystal structure analysis, revealing that the nucleophilic substitution of (E)-sulfonylethene with arylethynide underwent a selective stereoinversion. The (Z)-enediynes exhibited photoluminescence in both the solution and solid states (crystals and powders). Ph2N-substituted derivatives showed remarkable solvatofluorochromism, and upon replacing the solvent from toluene to acetonitrile, the emission color changed from blue to yellow.

Octanuclear Zinc Clusters in Microporous Organic Polymers: Network-Enhanced Reductive CO2 Fixation to Formamides at Room Temperature.

A building block containing eight zincs and eight iodo groups (8Zn) is obtained by the Zn complexation of a salen ligand bearing two additional hydroxy groups. Through the Sonogashira-Hagihara coupling of 8Zn with 1,3,5,7-tetra(4-ethynylphenyl) adamantane, microporous organic polymers bearing octanuclear zinc clusters (MOP-8Zn) are prepared, exhibiting a high surface area of 562 m2g-1, microporosity, and a particulate morphology with an average diameter of 249nm. The MOP-8Zn exhibits significantly enhanced catalytic performance, compared to molecular counterparts, in the reductive carbon dioxide fixation to formamides, possibly due to the cooperative adsorption and confinement effect of networks on substrates.

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.

Heterojunction of branched benzopyrazine-based polymers coating on graphene for electrochemical sensing of vanillin

Vanillin finds widespread applications in various industries, such as food, pharmaceuticals, and cosmetics. However, excessive intake of vanillin could pose risks to human health. This study detailed the successful creation of a heterojunction of branched benzopyrazine-based polymers coating on graphene (CMP-rGO) through the Sonogashira-Hagihara coupling reaction. Utilizing the CMP-rGO, a novel electrochemical sensor for vanillin detection was developed. Besides, the synthesized materials were validated using standard characterization techniques. Both cyclic voltammetry and differential pulse voltammetry techniques were employed to investigate vanillin's electrochemical characteristics on this sensor. The findings indicated a significant enhancement in vanillin's electrochemical signal responsiveness with the application of CMP-rGO. Under optimal conditions, the sensor demonstrated a linear response to vanillin concentrations ranging from 0.08 to 33 μM and achieved a detection limit as low as 0.014 μM. Also, the constructed electrochemical sensor exhibited excellent selectivity, stability, and reproducibility. It has been effectively employed to detect vanillin in real samples such as human serum, human urine, and vanillin tablets, with a recovery rate of 99.13–103.6 % and an RSD of 3.46–1.26 %. Overall, this innovative sensor offers a novel approach to the efficient and convenient detection of vanillin.

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.

Biomass betulin-based porous aromatic frameworks nanomicrospheres as adsorbents for reversible capture of iodine

Betulin with a modifiable hydroxyl group and a rigid backbone is a kind of natural triterpene product that extracted from white barked birch bark with up to 30 % of its dry weight. Herin, we prepared a series of betulin-based porous aromatic frameworks (BEPAFs) nanomicrospheres by [Rh(nbd)Cl]2 polymerization or Sonogashira-Hagihara coupling reaction for iodine vapor capture and adsorption. The resulting BEPAFs nanomicrospheres presented perfect thermal stability and high specific surface areas that up to 324.6 m2 g−1, 506.3 m2 g−1 and 320.5 m2 g−1 for BEPAF-1, BEPAF-2 and BEPAF-3, respectively. Based on the above characteristics, the BEPFAs nanomicrospheres showed an excellent iodine capture performance with the volatile iodine capture ability reached 3.79 g g−1 and iodine adsorption in cyclohexane solution up to 389.9 mg g−1. The iodine capture behavior is consistent with the pseudo-second-order model, indicating that the iodine adsorption process of BEPAFs microspheres belongs to multilayer heterogeneous surface chemical adsorption. Furthermore, the BEPFAs nanomicrospheres could maintained 88.26 % of the absorption capacity after four cycles that endow them a great potential in practical application. This research provides a facile synthesis of biomass porous aromatic framework nanomicrospheres adsorbents based on the natural product.

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.

Utilizing Hairy Hollow Conjugated Microporous Polymers and Native Enzymes for Precise Aerobic Photocatalysis Under Near‐Infrared Wavelengths

AbstractUtilizing photoregenerated cofactors in conjunction with enzymes in a sequential manner presents an effective approach for the synthesis of targeted compounds in gentle reaction conditions. Nevertheless, the integration of enzymes and photocatalysts has faced challenges due to the swift breakdown of biomaterials caused by high‐energy or blue lights and photoinduced reactive oxygen species, leading to the denaturation and deactivation of enzymatic materials. This study details the deliberate development and production of hairy hollow conjugated microporous polymers (S‐hPrTZ‐P HCMPs), achieved via Sonogashira–Hagihara coupling on SiO2 templates, followed by sulfonation, polymer grafting and ultimately eliminating the SiO2 cores. This technique leverages the distinctive characteristics of low‐energy near‐infrared light, such as its superior penetration ability, to effectively regenerate the enzymatic cofactor NAD+ from NADH. It can accomplish this feat even when faced with synthetic or biological barriers that are impermeable to visible light. Simultaneously, photogenerated reactive oxygen species are captured and neutralized by the hydrophilic polymer brushes, safeguarding the integrity of the enzymatic material. The adaptability of S‐hPrTZ‐P with photocatalytic properties is showcased alongside glucose 1‐dehydrogenase and glycerol dehydrogenase. This structure and morphology‐controlled strategy offers a promising pathway for various enzymatic photobiocatalysis employing stable, efficient, and reusable hairy HCMPs.

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.

Synthesis of conjugated microporous polymers rich in sulfonic acid groups for the highly efficient adsorption of Cs+

Conjugated microporous polymers (CMPs) with extended π-conjugated systems and permanent microporous scaffolders have broad application prospects in the treatment of radionuclides in nuclear wastewater. Herein, the Sonogashira–Hagihara coupling process was employed to generate three CMPs, called CMP1–3. CMP1S–3S with different degrees of sulfonation were produced and employed for Cs+ ion adsorption by adjusting the sulfonation time using chlorosulfonic acid as the sulfonating agent. This is the first attempt to apply CMPs containing sulfonic acid groups to Cs+ ion adsorption, which show excellent adsorption properties. CMP1S-48 with the highest surface sulfonic acid group density exhibited the fastest adsorption rate, and it reached adsorption equilibrium on Cs+ ion in an aqueous solution under 1 min. The adsorption process corresponded to the Freundlich isotherm model of multilayer adsorption, with an adsorption capacity of up to 288.1 mg g−1. Compare with CMP2S-48 and CMP3S-48, CMP1S-48 with more sulfonic acid groups shows the highest adsorption capacity. Moreover, the selectivity of CMP1S-48 adsorbing Cs+ ion was exceeded high. Notably, the adsorption mechanism of Cs+ ion by CMP1S–3S involved ion exchange with H+ in the sulfonic acid groups, as well as its complexation and electrostatic attraction with the sulfonic acid groups. This work opens up a new way for CMPs rich in sulfonic acid groups to treat Cs+ ion-contaminated water sources.

Bipyridine-containing π-conjugated polymers bearing optically active amide groups: mechanistic aspects of formation of chiral higher-order structures

A helically foldable bipyridine-containing poly(phenyleneethynylene) was synthesized by the Sonogashira–Hagihara coupling polymerization of N-(3,5-diethynylbenzoyl)-l-alanine dodecyl ester with 4,4′-dibromo-2,2′-bipyridine.

Synthesis of geometry-controlled platinum-containing polymers bearing optically active bidentate phosphine ligands

Pt-diyne polymers were synthesized by dehydrochlorination coupling polymerization of a cis-PtCl2 complex with 1,4-diethynylbenzene, and Sonogashira–Hagihara coupling polymerization of a cis-Pt diethynyl complex with 1,3- and 1,4-diiodobenzenes.

Rational design and synthesis of bifunctional Dibenzo[g,p]chrysene-based conjugated microporous polymers for energy storage and visible light-driven photocatalytic hydrogen evolution

The importance of conjugated microporous polymers (CMPs) as active components in photocatalytic hydrogen evolution is growing due to its intense ultraviolet–visible (UV–vis) absorption, potent fluorescence, and high carrier transport capacity, dibenzo[g,p]chrysene shows notable photophysical and electrical features. This is because CMPs have stiff molecular structures with large π-conjugation. In this section, we describe our approach and syntheses of three types of polymers for the first time to determine the reactivity of dibenzo[g,p]chrysene (TBN)-based CMPs for photocatalytic H2 evolution and energy storage applications. Three TBN-based CMPs, TBN-TBN (D-D), TBN-TBN-TPA (A-D), and TBN-TBN-BT (D-A), were synthesized via Sonogashira–Hagihara coupling. TBN-CMP materials were used as working electrodes for energy storage applications. The TBN-TBN-BT CMP demonstrated excellent capacity retention (98.2%) over 2000 cycles and high capacitor (130 F g−1) at 0.5 A g−1, in accordance with electrochemical performance. Furthermore, the hydrogen evolution rate (HER) results are in the following order 8452, 9800, and 3060 μmol g−1h−1 for TBN-TBN, TBN-TBN-TPA, and TBN-TBN-BT CMPs, respectively. These findings suggest that using TBN as an acceptor increases the number of active sites for proton reduction, thereby boosting the rate of H2 evolution.

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.

Electron-Rich Triazine-Conjugated Microporous Polymers for the Removal of Dyes from Wastewater.

Conjugated microporous polymers (CMP) as porous functional materials have received considerable attention due to their unique structures and fascinating properties for the adsorption and degradation of dyes. Herein, a triazine-conjugated microporous polymer material with rich N-donors at the skeleton itself was successfully synthesized via the Sonogashira-Hagihara coupling by a one-pot reaction. These two polymers had Brunauer-Emmett-Teller (BET) surface areas of 322 and 435 m2g-1 for triazine-conjugated microporous polymers (T-CMP) and T-CMP-Me, respectively. Due to the porous effects and the rich N-donor at the framework, it displayed a higher removal efficiency and adsorption performance compared to cationic-type dyes and selectivity properties for (methylene blue) MB+ from a mixture solution of cationic-type dyes. Furthermore, the T-CMP-Me could quickly and drastically separate MB+ and (methyl orange) MO- from the mixed solution within a short time. Their intriguing absorption behaviors are supported by 13C NMR, UV-vis absorption spectroscopy, scanning electron microscopy, and X-ray powder diffraction studies. This work will not only improve the development of porous material varieties, but also demonstrate the adsorption or selectivity of porous materials for dyes from wastewater.

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.

Solid state chemical transformation provides a fully benzoxazine-linked porous organic polymer displaying enhanced CO2 capture and supercapacitor performance

We synthesized a fully benzoxazine (BZ)-linked POP comprising TPA and DHPT units through Sonogashira–Hagihara coupling and ring opening polymerization for CO2 capture and energy storage.

Hydroboration of Hollow Microporous Organic Polymers: A Promising Postsynthetic Modification Method for Functional Materials.

This work shows that hydroboration can be efficiently applied to the postsynthetic modification (PSM) of the Sonogashira-Hagihara coupling-based microporous organic polymers (MOPs). Hollow MOPs (H-MOPs) were prepared by template synthesis through the Sonogashira-Hagihara coupling of tetra(4-ethynylphenyl)methane with 1,4-diiodobenzene. The H-MOPs were used as platforms in the PSM-based functionalization. The heat-treatment of H-MOPs in the presence of a neat pinacolborane reagent resulted in the successful addition of pinacolborane groups to the internal alkynes of H-MOPs, generating H-MOPs with pinacolboranes (H-MOP-BPs). The pinacolborane moieties in the H-MOP-BP were further converted to boronic acid groups. The resultant H-MOP-BAs were used as heterogeneous organocatalysts in the CO2 fixation with epoxides to cyclic carbonates at ambient temperature (50 °C). Moreover, H-MOP-BAs could be recycled with retention of the catalytic performance in five successive reactions.