Abundant interfacial defects remain a significant challenge that hampers both the efficiency and stability of perovskite solar cells(PSCs).Herein,an alcohol-dispersed conducting polymer complex,denoted as PEDOT:F(Poly...Abundant interfacial defects remain a significant challenge that hampers both the efficiency and stability of perovskite solar cells(PSCs).Herein,an alcohol-dispersed conducting polymer complex,denoted as PEDOT:F(Poly(3,4-ethylene dioxythiophene):Perfluorinated sulfonic acid ionomers),is introduced into the interface between perovskite and hole transporting layer in regular-structured PSCs.PEDOT:F serves as a multi-functional interface layer(filling grain boundaries and covering perovskite's grain-surface)to achieve a robust interaction with organic groups within perovskites,which could induce a structural transformation of PEDOT to increase its conductivity for the efficient hole-transport.Furthermore,the strong interaction between PEDOT and perovskites could promote an effective coupling of undercoordinated Pb~(2+)ions with the lone electron pairs near O&S atoms in PEDOT molecules,thereby enhancing defect passivation.Additionally,PEDOT:F with inherent hydrophobic properties prevents effectively moisture invasion into perovskites for the improved long-term stability of the PSCs.Consequently,the PEDOT:F-based PSCs achieved a champion efficiency of 24.81%,and maintained ca.92%of their initial efficiency after 7680 h of storage in a dry air environment,accompanied by the enhanced photothermal stability.展开更多
The catalysis of olefin polymerization through the chain-walking process is a subject of great interest. In this contribution, the successful synthesis of a Brookhart-type unsymmetrical α-diimine nickel catalyst Ni, ...The catalysis of olefin polymerization through the chain-walking process is a subject of great interest. In this contribution, the successful synthesis of a Brookhart-type unsymmetrical α-diimine nickel catalyst Ni, which contains both dibenzhydryl and phenyl groups, was determined by X-ray crystallography. The compound has a pseudo-tetrahedral geometry at the Ni center, showing pseudo-C2-symmetry. Upon activation with modified methylaluminoxane (MMAO), Ni1 exhibits high catalytic activity up to 1.02 × 107 g PE (mol Ni h)−1 toward ethylene polymerization, enabling the synthesis of high molecular weight branched polyethylene. The molecular weights and branching densities could be tuned over a very wide range. The polymerization results indicated the possibility of precise microstructure control, depending on the polymerization temperature. The branching densities were decreased with increasing the polymerization temperature.展开更多
Synthetic inorganic pigments are most widely used in ceramic applications due to their excellent chemical and thermal stability and their lower toxicity to both human and environment as well.In the present work,black ...Synthetic inorganic pigments are most widely used in ceramic applications due to their excellent chemical and thermal stability and their lower toxicity to both human and environment as well.In the present work,black ceramic pigment CoFe_(2)O_(4)has been synthesized by the complex polymerization method(CPM)with good chemical homogeneity.In order to study the influence of variables on the process of obtaining pigment through CPM,2^((5-2))fractional factorial design with resolution III was used.The variables studied in the mathematical modeling were:citric acid/metal concentration,pre-calcination time,calcination temperature,calcination time,and calcination rate.Powder pigments were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),and UV-visible(UV-Vis)spectroscopy.Based on the results,the formation of cobalt ferrite phase(CoFe_(2)O_(4))with spinel structure was verified.The color of pigments obtained showed dark shades,from black to gray.The model adjusted to the conditions proposed in this study due to the determination coefficient of 99.9%and variance(R²)showed that all factors are significant at the confidence level of 95%.展开更多
The polymeric ligand PBIa (functionalized polybenzimidazole containing β-diketone side group) was successfully synthesized via the reaction of polybenzimidazole (PBI) with 3-Br-acetylacetone in DM SO solvent usin...The polymeric ligand PBIa (functionalized polybenzimidazole containing β-diketone side group) was successfully synthesized via the reaction of polybenzimidazole (PBI) with 3-Br-acetylacetone in DM SO solvent using Nail as the deprotonation reagent. Its corresponding polymeric complexes of Dy^3+ and Gd^3+ were prepared and characterized by FT-IR, ^1H NMR, molar conductance measurements, and thermal analysis. The photoluminescence properties and the probable mechanism of the Dy and Gd complexes were studied. The measurement and analysis of the thermal properties showed that these were thermal stable.展开更多
A series of polymeric complexes were prepared from Fe^2+, Co^2+ or Ni^2+ and poly(Schiff base) (DAPcIPA), which was obtained by polycondensation of 5,6-diamino-1,10-phenanthroline (DAP) with isophthalaldehyde...A series of polymeric complexes were prepared from Fe^2+, Co^2+ or Ni^2+ and poly(Schiff base) (DAPcIPA), which was obtained by polycondensation of 5,6-diamino-1,10-phenanthroline (DAP) with isophthalaldehyde (IPA). The structures of the polymer and the polymeric complexes were characterized by IR, 1^H-NMR and elemental analysis. The magnetic behavior of these complexes was measured as a function of magnetic field strength (0-3.98 ~ 106 A/m) at 5 K and as a function of temperature (5-300 K) at a magnetic field strength of 2.39 × 10^6 A/re. Experimental results show that DAPcIPA-Ni^2+, DAPcIPA-Co^2+ are soft ferromagnets while DAPcIPA-Fe^2+ exhibits features of an antiferromagnet.展开更多
The polymerization of acrylonitrile initiated by organolanthanide complexes alone is studied for the first time. The effect of polymerization conditions on catalytic activity of the title complex and molecular weight ...The polymerization of acrylonitrile initiated by organolanthanide complexes alone is studied for the first time. The effect of polymerization conditions on catalytic activity of the title complex and molecular weight of the polymers produced have been studied.展开更多
A novel axially substituted silicon(IV) phthalocyanine, namely di-pyridyloxy axially substituted silicon(IV) phthalocyanine 2 was synthesized and characterized by UV/vis, IR, elemental analysis, MS as well as IH N...A novel axially substituted silicon(IV) phthalocyanine, namely di-pyridyloxy axially substituted silicon(IV) phthalocyanine 2 was synthesized and characterized by UV/vis, IR, elemental analysis, MS as well as IH NMR spectroscopy. Hydrophobic 2 was encapsulated by amphiphilic triblock copolymer poly[N^e-(benzyloxycarbonyl-lysine]-poly(ethylene glycol)-poly [N^e-(benzyl oxycarbonyl) (PLL(Z)-b-PEG-b-PLL(Z)) to form hydrophobic 2-loaded polymeric complex micelle (PIC) (2-loaded P/C). Atom force microscopy (AFM) image showed that 2-loaded PIC formed a spherical nanocarrier with approximately 35-50 nm in diameter. The fluorescence intensity and lifetime of 2-loaded PIC was significantly enhanced bv the incorporation 2 into PIC nanocarrier.展开更多
Polymerization of styrene and 1,3-butadiene were performed by calix[4]arene-neodymium complexes using di-n-butylmagnesium and tri-iso-butylaluminum as cocatalyst respectively. The effect of the substituent groups in c...Polymerization of styrene and 1,3-butadiene were performed by calix[4]arene-neodymium complexes using di-n-butylmagnesium and tri-iso-butylaluminum as cocatalyst respectively. The effect of the substituent groups in calix[4]arene on the catalytic activity was first investigated.展开更多
Polymerization of 4-vinylpyridine by complex catalyst of neodymium chloride was studied. The influence of Al/Nd (molar ratio), concentration of catalyst, reaction time and temperature on polymerization of 4-vinylpyrid...Polymerization of 4-vinylpyridine by complex catalyst of neodymium chloride was studied. The influence of Al/Nd (molar ratio), concentration of catalyst, reaction time and temperature on polymerization of 4-vinylpyridine was investigated. The results show that different kinds of ligand in the rare earth complex have an effect on the catalytic activity of the complex. The catalytic activity of the rare earth complex is higher than that of simple rare earth chloride. The catalytic activity of polymer-supported catalyst is higher than those of the similar small molecular system.展开更多
Neutral nickel sigma -acetylide complex [Ni(C=CPh)(2)(PBu3)(2)] is a novel initiator for the polymerization of styrene in CHCl3 over a range of polymerization temperature from 40 degreesC to 60 degreesC. The polystyre...Neutral nickel sigma -acetylide complex [Ni(C=CPh)(2)(PBu3)(2)] is a novel initiator for the polymerization of styrene in CHCl3 over a range of polymerization temperature from 40 degreesC to 60 degreesC. The polystyrene obtained was a syndio-rich atactic polymer and its weight-average molecular weight reached 279000. The mechanism of the polymerization was discussed and a radical mechanism was proposed.展开更多
The title complex 1,3-diphenyl-2-((quinolin-8-ylamino)methylene)propane-l,3- dione-palladium was synthesized by the reaction of 1,3-diphenyl-2-((quinolin-8-ylamino)-methylene)propane-1,3-dione with PdCl2, and ...The title complex 1,3-diphenyl-2-((quinolin-8-ylamino)methylene)propane-l,3- dione-palladium was synthesized by the reaction of 1,3-diphenyl-2-((quinolin-8-ylamino)-methylene)propane-1,3-dione with PdCl2, and characterized by IR spectrum and single-crystal X-ray diffraction analysis. The crystal belongs to the orthorhombic system, space group P21212 with a = 21.838(4), b = 8.3952(17), c = 11.497(2) A, V= 2107.9(7) A3, C25H17C1N2O2Pd, Mr = 519.26, Z= 4, Dc= 1.636 g/cm3, H = 1.032 mm-1, F (000) = 1040, the final R = 0.0307 and wR = 0.0778. This compound was investigated for the catalytic behavior towards norbornene (NB) vinyl addition polymerization. And the complex exhibits excellent catalytic activities up to 2.18×10^8g of PNB (tool of Pd)-1 h-1 with high monomer conversion using methylaluminoxane (MAO) as the cocatalyst.展开更多
A series of new nickel(Ⅱ)complexes with 2-aminomethylpyridine ligands,(2-PyCH_2NHAr)_2NiBr_2(Ar=2,6- dimethylphenyl 2a;2,6-diisopropylphenyl 2b,2,6-difluorophenyl 2c),have been synthesized and used as catalyst precur...A series of new nickel(Ⅱ)complexes with 2-aminomethylpyridine ligands,(2-PyCH_2NHAr)_2NiBr_2(Ar=2,6- dimethylphenyl 2a;2,6-diisopropylphenyl 2b,2,6-difluorophenyl 2c),have been synthesized and used as catalyst precursors for ethylene polymerization in the presence of methylaluminoxane(MAO).The catalysts containing ortho-alkyl-substituents afford high molecular weight branched polyethylenes as well as a certain amount of oligomers.Enhancing the steric bulk of the alkyl substituent of the catalyst resulted in...展开更多
The title complex bis{1-{[(6-ethyl-2-pyridinyl)imino]methylenyl}-2-naphthale- nolato-N,O}-nickel(lI) (C36H32NnO2Ni) has been synthesized by the reaction of l-{[(6-ethyl-2- pyridinyl)imino]methylenyl}-2-naphtha...The title complex bis{1-{[(6-ethyl-2-pyridinyl)imino]methylenyl}-2-naphthale- nolato-N,O}-nickel(lI) (C36H32NnO2Ni) has been synthesized by the reaction of l-{[(6-ethyl-2- pyridinyl)imino]methylenyl}-2-naphthalenol with Ni(CH3COO)2·4H2O, and characterized by IR spectrum, elemental analysis and TG. The complicated space structure has been confirmed by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 11.410(4), b = 14.382(4), c = 18.121(6) ,A, β = 97.147(6)% V= 2950.5(16)A3, C36H32N4O2Ni, Mr = 611.37, Z = 4, Dc = 1.376 g/cm3, μ = 0.698 mm-1 F(000) = 1280, the final R = 0.0519 and wR = 0.1493 (1 〉2σ(I)). This title compound was used as precatalysts for the polymerisation of norbornene. When activated with MAO, the complex exhibited excellent catalytic activity up to 1.98 × 107 g ofPNB (mol of Ni)-1 h-1 with high monomer conversion.展开更多
Two novel complexes, namely {[Cd(AIP)(4,4'-bpy)]·1.3DMF}n(1) and [Cd(AIP)(2,2'- bpy)]n(2), have been synthesized through solvothermal reaction(H2AIP = 5-aminoisophthalic acid, 2,2'-bpy = 2,2'-bip...Two novel complexes, namely {[Cd(AIP)(4,4'-bpy)]·1.3DMF}n(1) and [Cd(AIP)(2,2'- bpy)]n(2), have been synthesized through solvothermal reaction(H2AIP = 5-aminoisophthalic acid, 2,2'-bpy = 2,2'-bipyridine, 4,4'-bpy = 4,4'-bipyridine, and DMF = N,N'-dimethylformamide) and structurally determined by single-crystal X-ray diffraction. Complex 1 shows a three-dimensional(3D) layer-pillar framework with rectangular channels, while complex 2 displays a two-dimensional(2D) wave net architecture. Furthermore, 1 and 2 were characterized by elemental analysis, infrared spectra(IR), thermal gravimetric analyses(TGA) and fluorescence measurements. The luminescent properties of 1 dispersed in various organic solvents have been investigated systematically, demonstrating high selectivity for acetone via the fluorescence quenching effect.展开更多
A novel phenoxyimine-based Schiff base ligand and its mononuclear complex [C(58)H(52)N2NiO2](L = 2-benzhydryl-4-dimethoxy-3,5-dimethyl-salicylaldehyde) has been synthesized and characterized by IR spectrum, elem...A novel phenoxyimine-based Schiff base ligand and its mononuclear complex [C(58)H(52)N2NiO2](L = 2-benzhydryl-4-dimethoxy-3,5-dimethyl-salicylaldehyde) has been synthesized and characterized by IR spectrum, elemental analysis, TG, WAXD spectra, ^1H NMR and ^(13)C NMR. In addition, the molecular structure has been measured by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 14.510(6), b = 18.573(7), c = 20.961(6) A, β = 123.453(19)°, V = 4713(3)A^3, Mr = 867.73, Z = 4, Dc = 1.223 g/cm^3, μ = 0.456 mm^-1, F(000) = 1832, the final R = 0.0685 and wR = 0.1758(I 〉 2σ(I)). The complex was used as homogeneous catalysis of polymerization of norbornene, and the MAO as cocatalyst. The nickel complex exhibited good catalytic activity up to 1.913 × 10^7 g of PNB(mol of Ni)^-1h^-1,and the yields of these reactions depend on the nature of the substituent in the aromatic ring.展开更多
Phenyl isocyanate was for the first time successfully polymerized by divalent samarium complex (ArO)2Sm(THF)4. The monomer concentration and temperatur affected the polymerization greatly.
Novel polymeric Cu<sup>2+</sup> complexes derived from the reaction of cyanoacetylhydrazine (<strong>CAH</strong>;<strong>L</strong>) with CuCl<sub>2</sub>•2H<sub>...Novel polymeric Cu<sup>2+</sup> complexes derived from the reaction of cyanoacetylhydrazine (<strong>CAH</strong>;<strong>L</strong>) with CuCl<sub>2</sub>•2H<sub>2</sub>O in different solvents were synthesized and characterized. The isolated solid polymeric complexes were investigated using modern conventional physicochemical and spectral (IR, <sup>1</sup>H-NMR, UV-Vis. ESR, Raman), magnetic and thermal studies. The results revealed that <strong>CAH</strong> behaves in different ways towards the coordination of the Cu<sup>2+</sup> ion. The promotion of solvents to the cyano group was discussed on the basis of the solvent and the Cu<sup>2+</sup> ion used. Magnetic and spectral studies suggest octahedral geometry is proposed for the Cu<sup>2+</sup> complexes. EPR studies indicate the existence of polymeric complexes depending on the results of <i>g</i>-values. The results suggest that the number of copper atoms ranges from three to twelve atoms. The molecular modeling is drawn and some chemical characteristics are calculated such as chemical reactivity and energy components are investigated between the different types of the ligands.展开更多
An unbridged zirconocene complex bis(1,2-diphenylcyclopentadienyl)zirconium dichloride [(1,2-Ph2-C5H3)2ZrCl2] 1 has been synthesized and structurally characterized. When activated by MAO, 1 produces ultra-high molecul...An unbridged zirconocene complex bis(1,2-diphenylcyclopentadienyl)zirconium dichloride [(1,2-Ph2-C5H3)2ZrCl2] 1 has been synthesized and structurally characterized. When activated by MAO, 1 produces ultra-high molecular weight polyethylene with high melting transition temperature, as well as atactic oligopropylene with average molecular weight of ~1150 g mol-1.展开更多
Styrene-acrylic acid copolymer (SAAC)-supported iron complex (SAAC·Fe)was characterized and the effect of the characteristic parameters on the catalytic activity of the complex was investigated. IR spectrum sugge...Styrene-acrylic acid copolymer (SAAC)-supported iron complex (SAAC·Fe)was characterized and the effect of the characteristic parameters on the catalytic activity of the complex was investigated. IR spectrum suggested that the complex SAAC·Fe possesses a structure of(C)and the Fe-O bond is higher in covalency.The complex SAAC·Fe with the structure of(C)shoved a higher catalytic activity in butadiene polymerization. When Fe/-COOH molar ratio in SAAC·Fe was about 0.2 the complex gave optimum catalytic activity. The catalytic activity of SAAC·Fe with the higher content of long sequence of acrylic acid units was low. When the content of the short sequence of acrylic acid units was predominant and at the same time the content of the short sequence was approximately equal to that of the long sequence for stryrene, the activity of the complex was high.展开更多
基金supported by the Science Foundation(K201827)the Open Foundation of Hubei Key Laboratory of Optical Information and Pattern Recognition(202103,202206)the Graduate Education Innovation Fund of Wuhan Institute of Technology(CX2023279,CX2023277,CX2023272)。
文摘Abundant interfacial defects remain a significant challenge that hampers both the efficiency and stability of perovskite solar cells(PSCs).Herein,an alcohol-dispersed conducting polymer complex,denoted as PEDOT:F(Poly(3,4-ethylene dioxythiophene):Perfluorinated sulfonic acid ionomers),is introduced into the interface between perovskite and hole transporting layer in regular-structured PSCs.PEDOT:F serves as a multi-functional interface layer(filling grain boundaries and covering perovskite's grain-surface)to achieve a robust interaction with organic groups within perovskites,which could induce a structural transformation of PEDOT to increase its conductivity for the efficient hole-transport.Furthermore,the strong interaction between PEDOT and perovskites could promote an effective coupling of undercoordinated Pb~(2+)ions with the lone electron pairs near O&S atoms in PEDOT molecules,thereby enhancing defect passivation.Additionally,PEDOT:F with inherent hydrophobic properties prevents effectively moisture invasion into perovskites for the improved long-term stability of the PSCs.Consequently,the PEDOT:F-based PSCs achieved a champion efficiency of 24.81%,and maintained ca.92%of their initial efficiency after 7680 h of storage in a dry air environment,accompanied by the enhanced photothermal stability.
文摘The catalysis of olefin polymerization through the chain-walking process is a subject of great interest. In this contribution, the successful synthesis of a Brookhart-type unsymmetrical α-diimine nickel catalyst Ni, which contains both dibenzhydryl and phenyl groups, was determined by X-ray crystallography. The compound has a pseudo-tetrahedral geometry at the Ni center, showing pseudo-C2-symmetry. Upon activation with modified methylaluminoxane (MMAO), Ni1 exhibits high catalytic activity up to 1.02 × 107 g PE (mol Ni h)−1 toward ethylene polymerization, enabling the synthesis of high molecular weight branched polyethylene. The molecular weights and branching densities could be tuned over a very wide range. The polymerization results indicated the possibility of precise microstructure control, depending on the polymerization temperature. The branching densities were decreased with increasing the polymerization temperature.
基金support of the Brazilian research financing institutions:RECAM(Rede de Catalisadores Ambientais),CNPq,and CAPES.
文摘Synthetic inorganic pigments are most widely used in ceramic applications due to their excellent chemical and thermal stability and their lower toxicity to both human and environment as well.In the present work,black ceramic pigment CoFe_(2)O_(4)has been synthesized by the complex polymerization method(CPM)with good chemical homogeneity.In order to study the influence of variables on the process of obtaining pigment through CPM,2^((5-2))fractional factorial design with resolution III was used.The variables studied in the mathematical modeling were:citric acid/metal concentration,pre-calcination time,calcination temperature,calcination time,and calcination rate.Powder pigments were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),and UV-visible(UV-Vis)spectroscopy.Based on the results,the formation of cobalt ferrite phase(CoFe_(2)O_(4))with spinel structure was verified.The color of pigments obtained showed dark shades,from black to gray.The model adjusted to the conditions proposed in this study due to the determination coefficient of 99.9%and variance(R²)showed that all factors are significant at the confidence level of 95%.
基金Project supported by the Hunan Province Education Research Foundation of China (04C640)
文摘The polymeric ligand PBIa (functionalized polybenzimidazole containing β-diketone side group) was successfully synthesized via the reaction of polybenzimidazole (PBI) with 3-Br-acetylacetone in DM SO solvent using Nail as the deprotonation reagent. Its corresponding polymeric complexes of Dy^3+ and Gd^3+ were prepared and characterized by FT-IR, ^1H NMR, molar conductance measurements, and thermal analysis. The photoluminescence properties and the probable mechanism of the Dy and Gd complexes were studied. The measurement and analysis of the thermal properties showed that these were thermal stable.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.20374044 and 20434020).
文摘A series of polymeric complexes were prepared from Fe^2+, Co^2+ or Ni^2+ and poly(Schiff base) (DAPcIPA), which was obtained by polycondensation of 5,6-diamino-1,10-phenanthroline (DAP) with isophthalaldehyde (IPA). The structures of the polymer and the polymeric complexes were characterized by IR, 1^H-NMR and elemental analysis. The magnetic behavior of these complexes was measured as a function of magnetic field strength (0-3.98 ~ 106 A/m) at 5 K and as a function of temperature (5-300 K) at a magnetic field strength of 2.39 × 10^6 A/re. Experimental results show that DAPcIPA-Ni^2+, DAPcIPA-Co^2+ are soft ferromagnets while DAPcIPA-Fe^2+ exhibits features of an antiferromagnet.
文摘The polymerization of acrylonitrile initiated by organolanthanide complexes alone is studied for the first time. The effect of polymerization conditions on catalytic activity of the title complex and molecular weight of the polymers produced have been studied.
基金supported by the National Natural Science Foundation of China(No.20604007)Natural Science Foundation of Fujian(No.2008J0078)+1 种基金Key Foundation for Ministry of Education,China(No.206071)Project WKJ2008-2-61 supported by science research foundation of Ministry of Health & United Fujian Provincial Health and Education Project for Tackling the Key Research,China.
文摘A novel axially substituted silicon(IV) phthalocyanine, namely di-pyridyloxy axially substituted silicon(IV) phthalocyanine 2 was synthesized and characterized by UV/vis, IR, elemental analysis, MS as well as IH NMR spectroscopy. Hydrophobic 2 was encapsulated by amphiphilic triblock copolymer poly[N^e-(benzyloxycarbonyl-lysine]-poly(ethylene glycol)-poly [N^e-(benzyl oxycarbonyl) (PLL(Z)-b-PEG-b-PLL(Z)) to form hydrophobic 2-loaded polymeric complex micelle (PIC) (2-loaded P/C). Atom force microscopy (AFM) image showed that 2-loaded PIC formed a spherical nanocarrier with approximately 35-50 nm in diameter. The fluorescence intensity and lifetime of 2-loaded PIC was significantly enhanced bv the incorporation 2 into PIC nanocarrier.
基金The authors are indebted to the financial supports of the National Natural Science Foundation of China (No.20774078 and the Key Program No.20434020);the Special Funds for Major Basic Research Projects (G2005CB623802).
文摘Polymerization of styrene and 1,3-butadiene were performed by calix[4]arene-neodymium complexes using di-n-butylmagnesium and tri-iso-butylaluminum as cocatalyst respectively. The effect of the substituent groups in calix[4]arene on the catalytic activity was first investigated.
文摘Polymerization of 4-vinylpyridine by complex catalyst of neodymium chloride was studied. The influence of Al/Nd (molar ratio), concentration of catalyst, reaction time and temperature on polymerization of 4-vinylpyridine was investigated. The results show that different kinds of ligand in the rare earth complex have an effect on the catalytic activity of the complex. The catalytic activity of the rare earth complex is higher than that of simple rare earth chloride. The catalytic activity of polymer-supported catalyst is higher than those of the similar small molecular system.
文摘Neutral nickel sigma -acetylide complex [Ni(C=CPh)(2)(PBu3)(2)] is a novel initiator for the polymerization of styrene in CHCl3 over a range of polymerization temperature from 40 degreesC to 60 degreesC. The polystyrene obtained was a syndio-rich atactic polymer and its weight-average molecular weight reached 279000. The mechanism of the polymerization was discussed and a radical mechanism was proposed.
基金Supported by the Natural Science Foundation of Fujian Province(2010J01026)the Ministry of Education of China(No.208066)+1 种基金the Education Department of Fujian Province(JA07029)the State Key Laboratory of Structural Chemistry(No.20130013)
文摘The title complex 1,3-diphenyl-2-((quinolin-8-ylamino)methylene)propane-l,3- dione-palladium was synthesized by the reaction of 1,3-diphenyl-2-((quinolin-8-ylamino)-methylene)propane-1,3-dione with PdCl2, and characterized by IR spectrum and single-crystal X-ray diffraction analysis. The crystal belongs to the orthorhombic system, space group P21212 with a = 21.838(4), b = 8.3952(17), c = 11.497(2) A, V= 2107.9(7) A3, C25H17C1N2O2Pd, Mr = 519.26, Z= 4, Dc= 1.636 g/cm3, H = 1.032 mm-1, F (000) = 1040, the final R = 0.0307 and wR = 0.0778. This compound was investigated for the catalytic behavior towards norbornene (NB) vinyl addition polymerization. And the complex exhibits excellent catalytic activities up to 2.18×10^8g of PNB (tool of Pd)-1 h-1 with high monomer conversion using methylaluminoxane (MAO) as the cocatalyst.
基金the National Natural Science Foundation of China(Nos.20674097,20734004)the Ministry of Education of China(Foundation for Ph.D.Training).
文摘A series of new nickel(Ⅱ)complexes with 2-aminomethylpyridine ligands,(2-PyCH_2NHAr)_2NiBr_2(Ar=2,6- dimethylphenyl 2a;2,6-diisopropylphenyl 2b,2,6-difluorophenyl 2c),have been synthesized and used as catalyst precursors for ethylene polymerization in the presence of methylaluminoxane(MAO).The catalysts containing ortho-alkyl-substituents afford high molecular weight branched polyethylenes as well as a certain amount of oligomers.Enhancing the steric bulk of the alkyl substituent of the catalyst resulted in...
基金Supported by the Natural Science Foundation of Fujian Province(2010J01026)the Ministry of Education of China(No.208066)+1 种基金the Education Department of Fujian Province(JA07029)the State Key Laboratory of Structural Chemistry(No.20130013)
文摘The title complex bis{1-{[(6-ethyl-2-pyridinyl)imino]methylenyl}-2-naphthale- nolato-N,O}-nickel(lI) (C36H32NnO2Ni) has been synthesized by the reaction of l-{[(6-ethyl-2- pyridinyl)imino]methylenyl}-2-naphthalenol with Ni(CH3COO)2·4H2O, and characterized by IR spectrum, elemental analysis and TG. The complicated space structure has been confirmed by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 11.410(4), b = 14.382(4), c = 18.121(6) ,A, β = 97.147(6)% V= 2950.5(16)A3, C36H32N4O2Ni, Mr = 611.37, Z = 4, Dc = 1.376 g/cm3, μ = 0.698 mm-1 F(000) = 1280, the final R = 0.0519 and wR = 0.1493 (1 〉2σ(I)). This title compound was used as precatalysts for the polymerisation of norbornene. When activated with MAO, the complex exhibited excellent catalytic activity up to 1.98 × 107 g ofPNB (mol of Ni)-1 h-1 with high monomer conversion.
基金the National Natural Science Foundation of China(21501178)Natural Science Funds of Fujian Province(No.2014H0055)for financial support of this work
文摘Two novel complexes, namely {[Cd(AIP)(4,4'-bpy)]·1.3DMF}n(1) and [Cd(AIP)(2,2'- bpy)]n(2), have been synthesized through solvothermal reaction(H2AIP = 5-aminoisophthalic acid, 2,2'-bpy = 2,2'-bipyridine, 4,4'-bpy = 4,4'-bipyridine, and DMF = N,N'-dimethylformamide) and structurally determined by single-crystal X-ray diffraction. Complex 1 shows a three-dimensional(3D) layer-pillar framework with rectangular channels, while complex 2 displays a two-dimensional(2D) wave net architecture. Furthermore, 1 and 2 were characterized by elemental analysis, infrared spectra(IR), thermal gravimetric analyses(TGA) and fluorescence measurements. The luminescent properties of 1 dispersed in various organic solvents have been investigated systematically, demonstrating high selectivity for acetone via the fluorescence quenching effect.
基金Supported by the Ministry of Education of China(No.208066)the Education Department of Fujian Province(JA07029)the State Key Laboratory of Structural Chemistry(No.20130013)
文摘A novel phenoxyimine-based Schiff base ligand and its mononuclear complex [C(58)H(52)N2NiO2](L = 2-benzhydryl-4-dimethoxy-3,5-dimethyl-salicylaldehyde) has been synthesized and characterized by IR spectrum, elemental analysis, TG, WAXD spectra, ^1H NMR and ^(13)C NMR. In addition, the molecular structure has been measured by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 14.510(6), b = 18.573(7), c = 20.961(6) A, β = 123.453(19)°, V = 4713(3)A^3, Mr = 867.73, Z = 4, Dc = 1.223 g/cm^3, μ = 0.456 mm^-1, F(000) = 1832, the final R = 0.0685 and wR = 0.1758(I 〉 2σ(I)). The complex was used as homogeneous catalysis of polymerization of norbornene, and the MAO as cocatalyst. The nickel complex exhibited good catalytic activity up to 1.913 × 10^7 g of PNB(mol of Ni)^-1h^-1,and the yields of these reactions depend on the nature of the substituent in the aromatic ring.
文摘Phenyl isocyanate was for the first time successfully polymerized by divalent samarium complex (ArO)2Sm(THF)4. The monomer concentration and temperatur affected the polymerization greatly.
文摘Novel polymeric Cu<sup>2+</sup> complexes derived from the reaction of cyanoacetylhydrazine (<strong>CAH</strong>;<strong>L</strong>) with CuCl<sub>2</sub>•2H<sub>2</sub>O in different solvents were synthesized and characterized. The isolated solid polymeric complexes were investigated using modern conventional physicochemical and spectral (IR, <sup>1</sup>H-NMR, UV-Vis. ESR, Raman), magnetic and thermal studies. The results revealed that <strong>CAH</strong> behaves in different ways towards the coordination of the Cu<sup>2+</sup> ion. The promotion of solvents to the cyano group was discussed on the basis of the solvent and the Cu<sup>2+</sup> ion used. Magnetic and spectral studies suggest octahedral geometry is proposed for the Cu<sup>2+</sup> complexes. EPR studies indicate the existence of polymeric complexes depending on the results of <i>g</i>-values. The results suggest that the number of copper atoms ranges from three to twelve atoms. The molecular modeling is drawn and some chemical characteristics are calculated such as chemical reactivity and energy components are investigated between the different types of the ligands.
文摘An unbridged zirconocene complex bis(1,2-diphenylcyclopentadienyl)zirconium dichloride [(1,2-Ph2-C5H3)2ZrCl2] 1 has been synthesized and structurally characterized. When activated by MAO, 1 produces ultra-high molecular weight polyethylene with high melting transition temperature, as well as atactic oligopropylene with average molecular weight of ~1150 g mol-1.
文摘Styrene-acrylic acid copolymer (SAAC)-supported iron complex (SAAC·Fe)was characterized and the effect of the characteristic parameters on the catalytic activity of the complex was investigated. IR spectrum suggested that the complex SAAC·Fe possesses a structure of(C)and the Fe-O bond is higher in covalency.The complex SAAC·Fe with the structure of(C)shoved a higher catalytic activity in butadiene polymerization. When Fe/-COOH molar ratio in SAAC·Fe was about 0.2 the complex gave optimum catalytic activity. The catalytic activity of SAAC·Fe with the higher content of long sequence of acrylic acid units was low. When the content of the short sequence of acrylic acid units was predominant and at the same time the content of the short sequence was approximately equal to that of the long sequence for stryrene, the activity of the complex was high.