Sonogashira-Hagihara Cross-coupling Reaction Research Articles

Composite Flame Retardants Based on Conjugated Microporous Polymer Hollow Nanospheres with Excellent Flame Retardancy.

The development of polymer materials with excellent flame retardancy has been paid increasing attention for their valuable applications in saving energy in modern architecture. Herein, conjugated microporous polymers hollow nanospheres (CMPs-HNS) were prepared by Sonogashira-Hagihara cross-coupling reaction with 1,3,5-triacetylenebenzene, 3-amino-2,6-dibromopyridine, and 2,4,6-tribromoaniline as building blocks using SiO2 nanoparticles as hard templates. To enhance the flame-retardant performance of the CMPs-HNS, antimony pentoxide solution (Sb2O5) and bisphenol A-bis (diphenyl phosphate) (BDP) were coated onto the as-prepared CMP-HNS (CMPs-HNS-BSb) by a simple immersion method. The peak heat release (pHRR) from microscale combustion colorimeter (MCC) of CMPs-HNS-BSb was 76.5 and 73.05 W g-1, respectively. By introducing CMPs-HNS-BSb into the epoxy resin (EP) matrix, the CMP2-HNS-BSb/EP (0.5) composites show that the pHRR values were 809.3 and 645.2 kW m-2, reduced by 21% as measured by conical calorimetry (CC), and total heat release (THR) reduced by 29.7%, going from 101 to 70.8 MJ/m2 when compared to the pure sample. Besides, total smoke production (TSP) reduced about 23.7%. The hollow structure can enhance the thermal insulation performance. As measured, the thermal conductivity of CMP1-HNS-BSb and CMP2-HNS-BSb is 0.044 and 0.048 W m-1 K-1. Based on the advantages of simple manufacture, superior thermal insulation, and flame retardancy, our CMPs-HNS-BSb/EP composites may find useful applications in various aspects such as building energy saving in future development.

Synthesis of Regioregular and Random Boron-Fused Azomethine Conjugated Polymers for Film Morphology Control.

Regioregular and random conjugated polymers based on a boron-fused azomethine unit were synthesized by Sonogashira-Hagihara cross coupling reaction. Although these polymers exhibited similar optical properties in the solution states, a distinct difference was observed in the aggregation forming ability in the film states; scanning electron microscope (SEM) observation indicated the existence of fiber-like aggregates in the spin-coated film of the regioregular polymer, while regiorandom polymer showed no aggregate in the film state. Accordingly, the UV-vis absorption spectrum of the regioregular polymer showed an increased shoulder peak due to the aggregate formation, whereas the random one showed no change. Furthermore, an absolute fluorescence quantum efficiency of the regioregular polymer was enhanced in response to the aggregate disassembly via thermal annealing treatment. In this study, we demonstrate that controlling regioregularity of the conjugated polymers can induce the different morphological structures and thermal-responsive behaviors. These findings could be beneficial for the design strategy and potential applications of thin-film optoelectronic devices with stimuli-responsive properties.

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.

A hollow viologen-based porous organic polymer for the catalytic cycloaddition of CO2

Viologen-based porous organic polymers with a hollow structure were synthesizedviaa Sonogashira–Hagihara cross-coupling reaction. They showed excellent catalytic performance for the carbon-dioxide cycloaddition reaction.

Polypyrrole-coated conjugated microporous polymers/expanded graphene carbon aerogels based phase change materials composites for efficient energy conversion and storage

Phase change materials (PCMs) composites are of great importance for a wide range of applications in energy conversion and storage, waste heat recovery and utilization, thermal energy management in building, electronic devices cooling and heat insulation, etc. Herein, a novel strategy for the fabrication of PCM composites for solar/electro energy conversion and storage is reported. The polypyrrole (PPy) coated conjugated microporous polymers/expanded graphene (EG) carbon aerogels/HDA (PCMPECAs/HDA) composites were firstly obtained via Sonogashira–Hagihara cross-coupling reaction followed by a carbonization treatment, PPy coating and finally 1-Hexadecylamine (HDA) impregnation. The introduction of EG and PPy was to improve the porosity, thermal conductivity and photothermal performance. The resultant PCMPECAs/HDA composites exhibited excellent comprehensive performances, including relatively high thermal conductivity of up to 234.0% that of HDA, high energy storage density up to 205.10 kJ/kg, excellent shape and thermal stability and a remarkable photothermal conversion and storage efficiency of up to 93.5%, respectively. And after 300 times thermal and cooling cycles, the latent heat of PCMPECAs/HDA still remains up to 150.20 kJ/kg. Besides, the resultant composites also manifest excellent electro-thermal effect at low voltage. Due to the aforementioned advantages, PCMPECAs/HDA composites possess great potential applications in solar/electric energy conversion and storage. • Conjugated microporous polymer carbon aerogels composites are first reported. • The latent heat of PCMPECAs/HDA composites were tested up to 205.10 kJ/kg • The resultant composites show an ultrahigh photothermal conversion efficiency (93.5%). • The shape-stable composite has a phase change enthalpy of 150.20 kJ kg -1 after 300 cycles. • The resultant composites presented an excellent electro-thermal effect at low voltage.

Highly efficient removal of PM and VOCs from air by a self-supporting bifunctional conjugated microporous polymers membrane

Efficient removal of pollutants in the atmosphere is of great significance to human health and environmental restoration. Herein, we report the preparation of a self-supporting conjugated microporous polymers (CMPs) membrane (SS-CMPs-M) synthesized by Sonogashira-Hagihara (S–H) cross-coupling reaction using KBr tables as a template. The intrinsic hydrophobic chemical composition made it good hydrophobicity and lipophilicity, e.g., the water contact angles (WCA) for SS-CMPs-M were measured to be 113°. The aromatic building blocks of CMPs make SS-CMPs-M exceptionally stable physicochemical properties, i.e., the membrane exists stably below 300 °C, and they were insoluble in organic solvents. Additionally, the as-resulted SS-CMPs-M-1 which also presents mesoporous architecture shows effectively captures performance for particulate matter (PM) with different particle sizes in the air, the removal efficiency of PM2.5 and PM10 are 99.7% and 99.9%, respectively. For volatile organic compounds (VOCs) vapor in the air, the SS-CMPs-M-1 shows an excellent purification effect, the removal efficiency of formaldehyde in the simulated air is above 97%, and the AQI value of the filtered gas (>500) is reduced to 50. Taking advantage of its simple and scalable manufacture, the SS-CMPs-M-1 may have great potential as an advanced membrane for the separation and elimination of PM in different environments.

3D Binder-free conjugated microporous polymer carbon Aerogels@MnO2 cathode for High-Performance aqueous zinc ion batteries

Binder-free MnO2-based cathodes are critical to the development of aqueous Zn//MnO2 batteries. Here, conjugated microporous polymer aerogels (CMPAs) with columnar, rod and linear shapes are successfully prepared through Sonogashira-Hagihara cross-coupling reaction. Using them as precursors, we obtain the integrated high-conductivity carbon-based aerogels (C-CMPAs) by pyrolysis. Secondly, MnO2 nanosheet arrays are uniformly grown on the surface of C-CMPAs nanotubes(C-CMPAs@MnO2) form a thin-walled cell configuration through a simple low temperature hydrothermal method. In this system, C-CMPAs serve as both current supporter and collector, while the cross-linked MnO2 flakes act as the active layer. This unique anisotropic structure not only greatly enlarges the contact area of electrode/electrolyte interfaces and supplies abundant electrochemically active sites, but shortens the Zn2+ ion insertion/extraction paths. Meanwhile, the high mechanical strength of core/shell structure between C-CMPAs and MnO2 renders long-term cycling life. Finally, binder-free C-CMPAs@MnO2-based aqueous zinc-ion batteries provide an unprecedented capacity of 670.7 mAh g−1 at 0.1 A g−1, good rate performance and excellent cycle stability (94.1% after 600 cycles). More importantly, the Zn//C-CMPAs@MnO2 aqueous battery provides high energy density of 536.6 Wh kg−1 at 80.3 W kg−1, superior to most similar reports, indicating the great potential of high-performance rechargeable batteries.

Porphyrinic conjugated microporous polymer anode for Li-ion batteries

Porphyrin-based molecules have attracted considerable interests for using as anodes in Li-ion batteries, because of their large π-conjugated aromatic structures, abundant active sites with multi-electron redox activities, and narrow HOMO–LUMO gaps. Herein, a porphyrinic conjugated microporous polymer was prepared through the Sonogashira-Hagihara cross-coupling reaction of Br-functionalized porphyrinic monomer and alkynyl-based monomer. Due to the existence of abundant active sites, rich porosity, narrow bandgap, and inhibition of dissolution in electrolyte, this porphyrinic porous polymer can be used as anode material for Li-ion batteries, and achieves high specific capacity of 1200 mAh g−1 at 1 A g−1, and capacity retention of 242% after 5000 cycles at 3 A g−1. This excellent performance can bear comparison with that of the state-of-the-art organic anode materials. The ex situ X-ray photoelectron spectroscopy tests reveal all of the porphyrin center, benzene ring and alkynyl parts of the porous polymer can be acted as active sites for Li insertion during the cathodic process.

Direct chemical synthesis of nitrogen-doped graphynes with high supercapacitance via a cross-coupling copolymerization strategy

Development of graphyne-type carbon materials, which are constructed by different combination of sp2 and sp hybridized carbon atoms, has been a thriving research hotspot in material science, due to their promising application in a range of energy and environmental fields. Herein, nitrogen-doped graphyne materials (NGY-1 and NGY-2) were directly synthesized by Sonogashira-Hagihara cross-coupling reaction, using hydrogen-deficient multi-acetylene and polyhalide compounds as the comonomers. NGY-1 and NGY-2 possess two-dimensional porous structure, high nitrogen content and homogenous nitrogen distribution. After heat-treatment at the temperature of 800 °C, the obtained materials NGY-1–800 and NGY-2–800 demonstrate high supercapacitive energy storage performances with specific capacitances up to 312 F g−1 at 0.1 A g−1 and excellent cycling properties. Compared with NGY-1–800, NGY-2–800 obtained from the pyrazine-containing precursor, exhibits a better rate capability thanks to higher content of graphitic nitrogen doping. The copolymerization strategy developed here can potentially provide a rational design principle and open a new gateway for the construction of novel graphyne-type carbon materials for energy storage applications.

Hollow porous organic polymers spheres decorated with silver nanoparticles for sterilization and oil/water separation

The exploitation of high-performance antibacterial materials is of great importance for maintain public health and sustainable development of modern society. Here, we describe a facile approach for the preparation of conjugated microporous polymer hollow spheres (CMP1-HSs and CMP2-HSs) by using SiO2 nanoparticles as a template and 1,3,5-triethynybenzene and 3,7-dibromophenothiazin-5-ium, bromide for CMP2 and 1,3,5-triethynybenzene and 1,4-dibromobenzene for CMP1-HSs as building blocks via the Sonogashira-Hagihara cross-coupling reaction. The as-synthesized CMPs-HSs possess good thermal stability with a thermal decomposition temperature of up to 588 °C, high porosity (a BET specific surface area of approximately 556 m2 g−1) and a unique hollow spherical morphology with inner diameter of ca. 380 nm. Benefit from their intrinsic lipophilicity and hydrophobicity, the CMPs-HSs could act as a kind of ‘micro-tank’ which enable to capture and absorption of organics from water. Interestingly, the CMPs-HSs also show an antibacterial property with bromide. To further improve their antibacterial performance, silver nanoparticles were doped onto the CMPs-HSs (abbreviated as [email protected]). The as-resulted [email protected] exhibit excellent antimicrobial activity both for gram-negative, e.g. Escherichia coli, The minimum inhibitory concentration (MIC) value of CMP1 is 15 μg mL−1 that is the growth of E. coli could be inhibited entirely after 3 h treatment. Taking advantages of their superior wettability, excellent absorption and separation ability, unique hollow spherical morphology makes much more accessible external surface area for doping Ag nanoparticles, such [email protected] may hold great potentials as a kind of novel porous medium for organic pollution elimination, water treatment and antibacterial applications.

Co3O4 nanoparticles embedded in triple-shelled graphitic carbon nitride (Co3O4/TSCN): a new sustainable and high-performance hierarchical catalyst for the Pd/Cu-free Sonogashira–Hagihara cross-coupling reaction in solvent-free conditions

Co3O4 nanoparticles embedded in triple-shelled graphitic carbon nitride (Co3O4/TSCN): a new sustainable and high-performance hierarchical catalyst for the Pd/Cu-free Sonogashira–Hagihara cross-coupling reaction in solvent-free conditions

Macrocyclic Arenes-Based Conjugated Macrocycle Polymers for Highly Selective CO2 Capture and Iodine Adsorption.

Incorporating synthetic macrocycles with unique structures and distinct conformations into conjugated macrocycle polymers (CMPs) can endow the resulting materials with great potentials in gas uptake and pollutant adsorption. Here, four CMPs (CMP-n, n=1-4) capable of reversibly capturing iodine and efficiently separating carbon dioxide are constructed from per-triflate functionalized leaning tower[6]arene (LT6-OTf) and [2]biphenyl-extended pillar[6]arene (BpP6-OTf) via Pd-catalyzed Sonogashira-Hagihara cross-coupling reaction. Intriguingly, owing to the appropriate cavity size of LT6-OTf and the numerous aromatic rings in the framework, the newly designed CMP-4 possesses an outstanding I2 affinity with a large uptake capacity of 208 wt % in vapor and a great removal efficiency of 94 % in aqueous solutions. To our surprise, with no capacity to accommodate nitrogen, CMP-2 constructed from BpP6-OTf is able to specifically capture carbon dioxide at ambient conditions.

Salt-resistant solar still based on hollow sphere porous ionic polymers for desalination

The exploitation of photothermal materials (PM) with desired salt-resistance is significant importance for solar steam generation (SSG). Herein, a novel salt-resistant PM based on porous ionic polymers（PIPs）coated with acetylene black (AB) was prepared for efficient SSG (named as PIPs-AB). The PIPs were synthesized using alkynylbenzene and ionic monomers as building blocks by Sonogashira-hagihara cross coupling reaction, which show low thermal conductivity (0.1 W m−1 K−1) and super hydrophilicity (infiltration within 40 ms). By decorated with AB, an excellent light absorption of 90% for the as-prepared PIPs-AB was obtained. Coupling with their superior thermal insulation and desired water transportation ability, the as-prepared PIPs-AB exhibits superior solar conversion efficiency (85.4% under 1 sun illumination). Furthermore, the intrinsically ionic feature of PIPs, combining with the Janus structure composed of superhydrophilic PIPs monolith and hydrophobic AB coating, makes the PIPs-AB excellent salt-resistant ability, e.g. no salt accumulation was observed after 6 h duration at 1 sun irradiation. Taking the advantages of the inherently adjustable chemical composition and tunable porosity of PIPs, the results of this work may open an opportunity for rational design and preparation of high-performance PIPs-based PM with desired salt-resistance for real SSG applications.

Conjugated microporous polymer foams with excellent thermal insulation performance in a humid environment.

This work reported two monolithic conjugated microporous polymer (CMP) foams synthesized through the Sonogashira–Hagihara cross-coupling reaction without mechanical stirring. The as-synthesized (CMP-ED and CMP-PT) foams exhibited superior hydrophobicity and low apparent density of 58 mg cm−3 and 63 mg cm−3. In addition, CMP-ED displayed a low thermal conductivity of 34.04 mW m−1 K−1, which was comparable with commercial SiO2 aerogels (34.09 mW m−1 K−1) at 50% humidity conditions. When the environment humidity was raised from 50% to 70%, the thermal conductivity of CMP-ED and commercial SiO2 aerogels improved by 0.12% and 7%, respectively. Furthermore, XRD, FTIR, BET and TG were conducted to evaluate the bulk structure and stability of CMP-ED and CMP-PT. The results illustrated the thermal conductivity values were greatly affected by the pore structure of foams. And the strong hydrophobicity and the narrow pore structure were responsible for the good thermal insulation performance under humid conditions. Considering the low density, superhydrophobicity, excellent physicochemical stability and impervious thermal conductivity in a high humidity environment, this CMP-ED presented great potential as an insulating material in a humid environment.

Template-assisted preparation of conjugated microporous polymers membranes for selective separation

Efficient removal of organic contaminants from wastewater is of great importance for both water resource utilization and environmental remediation. Herein, we report the facile synthesis of conjugated microporous polymers (CMPs) membranes by employment of 1,3,5-triethynylbenzene (1,3,5-TEB) and 1,4-Dibromobenzene (DB) as building blocks and Pd (0)/CuI as catalyst through a Sonogashira-Hagihara crosscoupling reaction using anodic aluminum oxide (AAO) as template. The as-prepared CMPs/AAO composite membranes, which can be fabricated as both free-standing thin films and AAO supported composite membranes, show a honeycomb-like porous network structure with strong hydrophobic and oleophilic wettability. The CMPs/AAO composite membranes exhibit excellent performance for separation of organic contaminants from wastewater. e.g., the removal efficiency of dye can reach ca. 100% with a permeation flux of over 300 L m−2 h−1 bar−1. Furthermore, both the suspended oils and emulsion oils in water can be easily separated by the CMPs/AAO composite membranes with a separation efficiency of up to 99.4%, making them promising candidates as a porous platform with significant potentials for separation and water treatment applications.

Salt-Rejection Solar Absorbers Based on Porous Ionic Polymers Nanowires for Desalination.

The construction of photothermal materials with ideal salt tolerance has been a major subject for efficient solar desalination. Herein, a novel photothermal material based on porous ionic polymers (PIPs) nanowires is synthesized by Sonogashira-Hagihara cross-coupling reaction using ionic salt and alkynylbenzene as building blocks. The PIPs nanowires monolith shows abundant porosity with low density, leading a superior thermal insulation. The intrinsic superhydrophilicity of PIPs nanowires endows it with desired water transportation ability. By facile spraying Chinese carbon-ink on the PIPs nanowires monolith, its light absorption can be enhanced to be 90%. Based on these merits, the PIPs nanowires based photothermal materials show high solar energy conversion efficiency (81% under 1 sun irradiation). More interestingly, its inherently ionic framework can result in an ion-ion interaction between the external ions in water and ionic groups in PIPs framework, thus leading to excellent desalination ability by combing its unique superhydrophilicity, for example, no salt accumulation is observed after 6 h duration at 1 sun irradiation. Compared with the existing salt-resistant photothermal materials, the method takes the advantage of the intrinsically ionic feature of PIPs without using any artificial process, thus may open a new way for design and fabrication of high-performance salt-rejection photothermal materials.

Facile preparation of composite flame retardantbased on conjugated microporous polymer hollow spheres

The development of functional materials with better flame-retardant and thermal insulation properties has attracted considerable attention for energy storage applications in modern society. Here, we describe a facile approach for the preparation of conjugated microporous polymer hollow spheres (CMP-HSs) by using SiO2 nanoparticles as a template via the Sonogashira-Hagihara cross-coupling reaction. The as-synthesized CMP-HSs have good thermal stability with a thermal decomposition temperature of up to 281 °C, high porosity (the BET specific surface area is measured to be approximately 666 m2 g−1) along with lipophilic and hydrophobic characteristics. To further improve their flame retardancy, CMP-HSs were treated with dimethyl phosphonate (DMMP) though an immersion method to prepare the CMP-HSs composite (CMP-HSs-DMMP) flame-retardants. By introducing CMP-HSs-DMMP into the epoxy resin (EP) matrix, the as-prepared EP composites showed excellent flame-retardant properties, e.g., the peak heat release rate (pHRR) and total heat release (THR) value of EP composites containing only 0.2% CMP-HSs-DMMP flame-retardant were 650.9 kW m−2 and 79.4 MJ m−2 respectively, in the range of 0 °C − 650 °C, which are 19.6 ± 2% and 19.1 ± 5% lower than that of pure EP within the same temperature range. Considering the significant enhancement of its flame retardancy with only a slight dosage of CMP-HSs-DMMP, such CMP hollow sphere-based flame-retardant composites may have great potential as functional bulk materials or coatings in a variety of fireproofing applications.

Acid Functionalized Conjugated Microporous Polymers as a Reusable Catalyst for Biodiesel Production

A series of conjugated microporous polymers (CMPs) based on bromophenol blue (BB) and bromocresol green (BG) have been synthesized via the Sonogashira–Hagihara cross-coupling reaction with surface ...

Conjugated microporous polymers bearing isocyanurate moiety as efficient antibacterial membrane and aerogels

The development of high-performance antibacterial materials is of great importance for human survival and health. Herein, we report the exploitation of novel conjugated microporous polymers bearing isocyanurate moiety (I-CMPs), which were synthesized using trichloroisocyanuric acid and ethynylbenzene as building blocks via Sonogashira-Hagihara cross-coupling condensation reaction, as efficient antibacterial materials. The as-resulted I-CMPs exhibit excellent antimicrobial activity both for gram-positive and gram-negative strains, e.g., The MBC value of I-CMPs is 250 μg·ml−1 that is the growth of E. coli and S. aureus could be inhibited entirely after 2 h treatment. The mechanism of the antibacterial process was preliminarily discussed. Furthermore, I-CMPs can be synthesized as monolithic nanofoam or free-standing film by facile varying the synthesis conditions for filtration or sterilization, e.g., E. coli in water (103 cfu·ml−1) could be captured entirely and quickly killed by filtration with I-CMPs monolithic nanofoam, which is of great technological significance with remarkable potentials for practical applications. These findings may also open a new route to rational design and creation of functional CMPs films or monolithic nanofoam with antimicrobial activity for a particular purpose.

Sulfur and nitrogen in-situ co-doped hierarchical spherical porous carbon for efficient lithium storage

A new strategy is presented to fabricate sulfur and nitrogen in-situ co-doped hierarchical spherical porous carbon (SNHSPC) and porous carbon nanotube (PCNT) from conjugated microporous polymer using alkynyl monomers and dibromine aromatic compounds as the building blocks through Sonogashira–Hagihara cross-coupling reactions for efficient lithium storage. SEM, XRD, TEM, XPS, nitrogen adsorption/desorption analysis and Raman spectrum were used to determine the structure of SNHSPC and PCNT. SNHSPC is hierarchical spherical porous carbon particles constituted by aggregated porous nano-fibers, which is distinctly different from those of PCNT. SNHSPC feature hierarchical spherical porous carbon, high specific surface area and homogeneous S and N co-doping, which enable a superior lithium storage behavior. The synergy of hierarchically porous structure and dual heteroatoms make SNHSPC afford a high lithium storage capacity, outstanding cycling stability and large rate performance, which are all superior to those of PCNT. The initial reversible capacity of SNHSPC is as high as 776 mA h g−1 at 0.1 A g−1.