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 high-purity and superfine high-entropy zirconate nanopowders,namely(Y_(0.25)La_(0.25)Sm_(0.25)Eu_(0.25))_(2)Zr_(2)O_(7)nanopowders,without agglomeration,were successfully synthesized via polymerized complex method...The high-purity and superfine high-entropy zirconate nanopowders,namely(Y_(0.25)La_(0.25)Sm_(0.25)Eu_(0.25))_(2)Zr_(2)O_(7)nanopowders,without agglomeration,were successfully synthesized via polymerized complex method at low temperatures for the first time.The results showed that the crystallinity degree,lattice strain,and particle size of the as-synthesized powders were gradually enhanced with the increase of the synthesis temperature from 800 to 1300℃.The as-synthesized powders involved fluorite phase in the range of 800-1200℃while they underwent the phase evolution from fluorite to pyrochlore at 1300℃.It is worth mentioning that the as-synthesized powders at 900℃are of the highest quality among all the as-synthesized powders,which is due to the fact that they not only possess the particle size of 11 nm without agglomeration,but also show high purity and good compositional uniformity.展开更多
Fe-, Y-Fe-Al- and Y-Ce-Fe- citrates were synthesized in ethylene glycol (EG) medium under conditions similar to those used in the polymerized complex method. Their elemental composition, IR,^ 13C and ^1H NMR, X-ray ...Fe-, Y-Fe-Al- and Y-Ce-Fe- citrates were synthesized in ethylene glycol (EG) medium under conditions similar to those used in the polymerized complex method. Their elemental composition, IR,^ 13C and ^1H NMR, X-ray photoelectron and Mossbauer spectra were studied, and formulae describing their composition were proposed. The complexes contained EG bonded as adduct and ester with citric acid ligand and did not contain ligands with deprotonated alcoholic groups. The complexes consisted of agglomerated spheres, 0.7-3 μm in diameter. The local composition of the products was established by energy dispersive X-ray microanalysis. The comparison of the number of the ligands, their average electrical charge and the esterification degree of mono-, di- and trimetallic complexes proved the mixed-metal nature of the species studied. The thermal decomposition of the complexes was studied and a general scheme of the processes taking place was proposed. Highly crystalline, phase homogeneous YaFe4AlO12 was produced after heating the respective complex at 1000 ℃. Ce-doped yttrium-iron garnet, similarly prepared, contained traces of CeO2.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 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 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
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
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 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
Two novel copper complexes with methyl or trifluoro-substituted mono-β-diiminato ligands and one acetoxyl anion were synthesized and characterized by IR spectroscopy and elemental analysis for the first time. The str...Two novel copper complexes with methyl or trifluoro-substituted mono-β-diiminato ligands and one acetoxyl anion were synthesized and characterized by IR spectroscopy and elemental analysis for the first time. The structure of complex 2 bearing trifluoro substituents was further confirmed by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 7.377(4), b = 11.727(6), c = 12.913(7) ?, α = 116.569(6), β = 98.829(7), γ = 96.520(6)°, V = 966.2(8) ?3, Z = 2, Mr = 479.86, Dc = 1.649 g/cm3, F(000) = 482, μ = 1.205 mm-1, the final R = 0.0370 and w R = 0.0903 for 3430 observed reflections with I 〉 2σ(I). These mono-β-diiminato copper complexes can effectively catalyze methacrylate(MA) polymerization when activated by MMAO. The introduction of fluoro groups into the N-aryl ring of β-diiminato ligands can greatly increase the catalytic activity of copper complexes as well as the molecular weight of PMA.展开更多
A new 1-D coordination polymer [Cd(Hsal)2(bpp)2] 1 was hydrothermally synthesi- zed by self-assembly of the corresponding metal oxide and salicylic acid (H2sal) with exo-bidentate flexible dipyridyl ligand 1,3-...A new 1-D coordination polymer [Cd(Hsal)2(bpp)2] 1 was hydrothermally synthesi- zed by self-assembly of the corresponding metal oxide and salicylic acid (H2sal) with exo-bidentate flexible dipyridyl ligand 1,3-bis(4-pyridyl)propane (bpp). X-ray crystal structure analysis reveals that complex 1 crystallizes in monoclinic,space group C2/c with a = 18.942(3),b = 12.9309(19),c = 16.504(2) A,β = 120.072(2)°,V = 3498.3(9)A^3,Z = 4,C40H38CdN4O6,Mr = 783.14,Dc = 1.487 g/cm^3,μ = 0.679 mm^-1,F(000) = 1608,R = 0.0619 and wR = 0.1435 for 3153 observed reflections (I 〉 2σ(I)). The most remarkable feature of 1 lies in the 1-D chain by repeating [Cd2(bpp)2] units which consist of a 24-membered macrocyclic ring. The 1-D motifs are further connected by C–H… O hydrogen bonds to generate a 2-D structure. In addition,thermal stability and luminescent property of compound 1 were also documented.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
The title complex bis{4-chloro-2-[(6-methyl-pyridin-2-ylimino)-methyl]-phenol}-palladium(Ⅱ)(C_(26)H_(20)Cl_2N_4O_2Pd) has been synthesized by the reaction of 4-chloro-2-[(6-methylpyridin- 2-ylimino)-methy...The title complex bis{4-chloro-2-[(6-methyl-pyridin-2-ylimino)-methyl]-phenol}-palladium(Ⅱ)(C_(26)H_(20)Cl_2N_4O_2Pd) has been synthesized by the reaction of 4-chloro-2-[(6-methylpyridin- 2-ylimino)-methyl]-phenol with Pd(CH_3COO)_2, and characterized by IR spectrum and elemental analysis. Single-crystal X-ray diffraction analysis results further confirmed the molecular structures. The crystal belongs to the monoclinic system, space group P2_1/c with a = 4.1324(2), b = 23.5432(16), c = 11.8943(8) A, β = 91.238(5)o, V = 1156.93(12) ?~3, C_(26)H_(20)Cl_2N_4O_2Pd, M_r = 597.76, Z = 2, D_c = 1.716 g/cm^3, μ = 1.067 mm^(-1), F(000) = 600, the final R = 0.0247 and w R = 0.0677(I 〉 2σ(I)). In the presence of methylaluminoxane(MAO), the complex exhibits excellent catalytic activities(1.737×10~7 g of PNB(mol of Pd)^(-1)·h^(-1)) in the vinyl polymerization of norbornene.展开更多
N-2-Thiazolylacrylamide (NTA) was polymerized by a radical route to obtain the polymer in good yield. The polymer with a pendent heterocyclic group is soluble in common organic solvents, which allow to prepare the c...N-2-Thiazolylacrylamide (NTA) was polymerized by a radical route to obtain the polymer in good yield. The polymer with a pendent heterocyclic group is soluble in common organic solvents, which allow to prepare the corresponding metal complexes with higher loads easily. FTIR, ^1H NMR, elemental analysis, and energy-dispersive X-Ray spectroscopy (EDX) were applied to characterize these materials. The magnetic behavior of Fe(Ⅱ) and Nd(Ⅲ) complexes of poly(N-2-thiazolylacrylamide) was examined by a PPMS-9T magnetometer, exhibiting the characteristics of a soft ferromagnet. It is found that the Nd(Ⅲ) complex has an extremely high relative saturation magnetization of 35 emu/g.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.
The properties of immobilized glucose oxidase (GOD) by the complexes of diethylaminoethyl cellulose(DEAEC) with different polymers, such as polymethylacrylic acid (PMAA), polyacrylic acid (PAA), polystyrene sulfonic a...The properties of immobilized glucose oxidase (GOD) by the complexes of diethylaminoethyl cellulose(DEAEC) with different polymers, such as polymethylacrylic acid (PMAA), polyacrylic acid (PAA), polystyrene sulfonic acid (PSSA), polyvinylaleohol (PVA), polyethylene oxide (PEO) and styrene-maleic acid copolymer (PSMA) were investigated. The activity of immobilized GOD was obviously influenced by the component of the DEAEC complexes. The relative activity of the immobilized GOD reached to maximum and over 90% of the native GOD. when the DEAEC-PMAA DEAEC-PAA complexes were used as a carrier with the molar ratio of DEAEC and polyacid of about one. Michaelis constants (Km) of the immobilized enzymes of DEAEC-GOD-PMAA and DEAEC-GOD-PAA were determined to be 1.25 and 1.00, respectively. Moreover, the immobilized GOD has a good storage stability and cyclic life.展开更多
This study is concerned with chitosan-polyacrylic acid complex as a carrier to immobilize glucose oxidase (GOD)and cellulase. The optimum emperature of the immobilized GOD (IG) was determined to be 60℃ which is highe...This study is concerned with chitosan-polyacrylic acid complex as a carrier to immobilize glucose oxidase (GOD)and cellulase. The optimum emperature of the immobilized GOD (IG) was determined to be 60℃ which is higher than that of the native GOD about 40℃. The optimum temperature of the immobilized cellulase (IC) was determined to be about 30℃ higher than that of native cellulase. Both of the optimum pH of IG and IC shifted one pH unit to acid. Immobilized enzyme may be used in more wide pH range. Their storage life are much longer compared with their native states. Both of them can be reused at least 12 times.展开更多
Polymer Ru-Co bimetallic complexes have been examined by X-ray photoelectron spectroscopy.The catalyst is highly active only when the mole ratio of Co/Ru is 4: 3. The activity of catalysts does not depend on the total...Polymer Ru-Co bimetallic complexes have been examined by X-ray photoelectron spectroscopy.The catalyst is highly active only when the mole ratio of Co/Ru is 4: 3. The activity of catalysts does not depend on the total Co/Ru ratio, but on the surface stoichiometry of Co and Ru. When the relative intensities of Co_2_p and Ru_(3d) of XPS peaks are close to each other and both are high,the catalyst exhibits its maximum activity The mechanism ofcatalytic hydroformylation has been discussed.展开更多
A new polymeric cobalt complex [Co(-male)(py)(H2O)]n (male = maleate; py = pyridine) 1 was prepared by cobalt chloride hexahydrate with disodium maleate and pyridine in an alcohol-aqueous solution. Single-crystal X-ra...A new polymeric cobalt complex [Co(-male)(py)(H2O)]n (male = maleate; py = pyridine) 1 was prepared by cobalt chloride hexahydrate with disodium maleate and pyridine in an alcohol-aqueous solution. Single-crystal X-ray analysis has revealed that 1 crystallizes in the orthor- hombic system, space group Pnma with a = 18.001(1), b = 7.6001(6), c = 7.4731(6) ? V = 1022.4(1) 3, Z = 4, C9H9CoNO5, Mr = 270.10, Dc = 1.755 g/cm3, F(000) = 548, m(MoK? = 1.683 mm-1, S = 1.002, the final R = 0.0280 and wR = 0.0746 for 883 observed reflections with I > 2s(I). The structure analysis shows an approximate octahedral coordination environment of metal center. The Co(II) ions are bridged by maleic anions in a rare tetradentate coordination fashion with a syn-anti coplanar con- formation of the carboxyl group, forming a two-dimensional corrugated 2-D structure which is further attached into a three-dimensional framework via non-classical CH…O interactions between adjacent layers.展开更多
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
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.
基金support from the National Natural Science Foundation of China(Nos.52122204 and 51972116)the Guangdong Basic and Applied Basic Research Foundation(Nos.2019A1515012145 and 2021A1515010603)+1 种基金the Fundamental Research Foundation for the Central Universities(No.2020ZYGXZR080)the Creative Research Foundation of the Science and Technology on Thermostructural Composite Materials Laboratory(No.JCKYS2020607003).
文摘The high-purity and superfine high-entropy zirconate nanopowders,namely(Y_(0.25)La_(0.25)Sm_(0.25)Eu_(0.25))_(2)Zr_(2)O_(7)nanopowders,without agglomeration,were successfully synthesized via polymerized complex method at low temperatures for the first time.The results showed that the crystallinity degree,lattice strain,and particle size of the as-synthesized powders were gradually enhanced with the increase of the synthesis temperature from 800 to 1300℃.The as-synthesized powders involved fluorite phase in the range of 800-1200℃while they underwent the phase evolution from fluorite to pyrochlore at 1300℃.It is worth mentioning that the as-synthesized powders at 900℃are of the highest quality among all the as-synthesized powders,which is due to the fact that they not only possess the particle size of 11 nm without agglomeration,but also show high purity and good compositional uniformity.
文摘Fe-, Y-Fe-Al- and Y-Ce-Fe- citrates were synthesized in ethylene glycol (EG) medium under conditions similar to those used in the polymerized complex method. Their elemental composition, IR,^ 13C and ^1H NMR, X-ray photoelectron and Mossbauer spectra were studied, and formulae describing their composition were proposed. The complexes contained EG bonded as adduct and ester with citric acid ligand and did not contain ligands with deprotonated alcoholic groups. The complexes consisted of agglomerated spheres, 0.7-3 μm in diameter. The local composition of the products was established by energy dispersive X-ray microanalysis. The comparison of the number of the ligands, their average electrical charge and the esterification degree of mono-, di- and trimetallic complexes proved the mixed-metal nature of the species studied. The thermal decomposition of the complexes was studied and a general scheme of the processes taking place was proposed. Highly crystalline, phase homogeneous YaFe4AlO12 was produced after heating the respective complex at 1000 ℃. Ce-doped yttrium-iron garnet, similarly prepared, contained traces of CeO2.
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.
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 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.
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 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.
基金Supported by the National Natural Science Foundation of China(21172269)the Applied Fundamental Research Project of Wuhan City(2015011701011598)
文摘Two novel copper complexes with methyl or trifluoro-substituted mono-β-diiminato ligands and one acetoxyl anion were synthesized and characterized by IR spectroscopy and elemental analysis for the first time. The structure of complex 2 bearing trifluoro substituents was further confirmed by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 7.377(4), b = 11.727(6), c = 12.913(7) ?, α = 116.569(6), β = 98.829(7), γ = 96.520(6)°, V = 966.2(8) ?3, Z = 2, Mr = 479.86, Dc = 1.649 g/cm3, F(000) = 482, μ = 1.205 mm-1, the final R = 0.0370 and w R = 0.0903 for 3430 observed reflections with I 〉 2σ(I). These mono-β-diiminato copper complexes can effectively catalyze methacrylate(MA) polymerization when activated by MMAO. The introduction of fluoro groups into the N-aryl ring of β-diiminato ligands can greatly increase the catalytic activity of copper complexes as well as the molecular weight of PMA.
基金Supported by the National Natural Science Foundation of China (No. 20771006)Education Committee of Anhui Province (KJ2008B005)
文摘A new 1-D coordination polymer [Cd(Hsal)2(bpp)2] 1 was hydrothermally synthesi- zed by self-assembly of the corresponding metal oxide and salicylic acid (H2sal) with exo-bidentate flexible dipyridyl ligand 1,3-bis(4-pyridyl)propane (bpp). X-ray crystal structure analysis reveals that complex 1 crystallizes in monoclinic,space group C2/c with a = 18.942(3),b = 12.9309(19),c = 16.504(2) A,β = 120.072(2)°,V = 3498.3(9)A^3,Z = 4,C40H38CdN4O6,Mr = 783.14,Dc = 1.487 g/cm^3,μ = 0.679 mm^-1,F(000) = 1608,R = 0.0619 and wR = 0.1435 for 3153 observed reflections (I 〉 2σ(I)). The most remarkable feature of 1 lies in the 1-D chain by repeating [Cd2(bpp)2] units which consist of a 24-membered macrocyclic ring. The 1-D motifs are further connected by C–H… O hydrogen bonds to generate a 2-D structure. In addition,thermal stability and luminescent property of compound 1 were also documented.
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The title complex bis{4-chloro-2-[(6-methyl-pyridin-2-ylimino)-methyl]-phenol}-palladium(Ⅱ)(C_(26)H_(20)Cl_2N_4O_2Pd) has been synthesized by the reaction of 4-chloro-2-[(6-methylpyridin- 2-ylimino)-methyl]-phenol with Pd(CH_3COO)_2, and characterized by IR spectrum and elemental analysis. Single-crystal X-ray diffraction analysis results further confirmed the molecular structures. The crystal belongs to the monoclinic system, space group P2_1/c with a = 4.1324(2), b = 23.5432(16), c = 11.8943(8) A, β = 91.238(5)o, V = 1156.93(12) ?~3, C_(26)H_(20)Cl_2N_4O_2Pd, M_r = 597.76, Z = 2, D_c = 1.716 g/cm^3, μ = 1.067 mm^(-1), F(000) = 600, the final R = 0.0247 and w R = 0.0677(I 〉 2σ(I)). In the presence of methylaluminoxane(MAO), the complex exhibits excellent catalytic activities(1.737×10~7 g of PNB(mol of Pd)^(-1)·h^(-1)) in the vinyl polymerization of norbornene.
基金This project is financially supported by the National Natural Science Foundation of China(No.20374044,20434020)
文摘N-2-Thiazolylacrylamide (NTA) was polymerized by a radical route to obtain the polymer in good yield. The polymer with a pendent heterocyclic group is soluble in common organic solvents, which allow to prepare the corresponding metal complexes with higher loads easily. FTIR, ^1H NMR, elemental analysis, and energy-dispersive X-Ray spectroscopy (EDX) were applied to characterize these materials. The magnetic behavior of Fe(Ⅱ) and Nd(Ⅲ) complexes of poly(N-2-thiazolylacrylamide) was examined by a PPMS-9T magnetometer, exhibiting the characteristics of a soft ferromagnet. It is found that the Nd(Ⅲ) complex has an extremely high relative saturation magnetization of 35 emu/g.
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.
基金This project is supported by the National Natural Science Foundation of China
文摘The properties of immobilized glucose oxidase (GOD) by the complexes of diethylaminoethyl cellulose(DEAEC) with different polymers, such as polymethylacrylic acid (PMAA), polyacrylic acid (PAA), polystyrene sulfonic acid (PSSA), polyvinylaleohol (PVA), polyethylene oxide (PEO) and styrene-maleic acid copolymer (PSMA) were investigated. The activity of immobilized GOD was obviously influenced by the component of the DEAEC complexes. The relative activity of the immobilized GOD reached to maximum and over 90% of the native GOD. when the DEAEC-PMAA DEAEC-PAA complexes were used as a carrier with the molar ratio of DEAEC and polyacid of about one. Michaelis constants (Km) of the immobilized enzymes of DEAEC-GOD-PMAA and DEAEC-GOD-PAA were determined to be 1.25 and 1.00, respectively. Moreover, the immobilized GOD has a good storage stability and cyclic life.
文摘This study is concerned with chitosan-polyacrylic acid complex as a carrier to immobilize glucose oxidase (GOD)and cellulase. The optimum emperature of the immobilized GOD (IG) was determined to be 60℃ which is higher than that of the native GOD about 40℃. The optimum temperature of the immobilized cellulase (IC) was determined to be about 30℃ higher than that of native cellulase. Both of the optimum pH of IG and IC shifted one pH unit to acid. Immobilized enzyme may be used in more wide pH range. Their storage life are much longer compared with their native states. Both of them can be reused at least 12 times.
文摘Polymer Ru-Co bimetallic complexes have been examined by X-ray photoelectron spectroscopy.The catalyst is highly active only when the mole ratio of Co/Ru is 4: 3. The activity of catalysts does not depend on the total Co/Ru ratio, but on the surface stoichiometry of Co and Ru. When the relative intensities of Co_2_p and Ru_(3d) of XPS peaks are close to each other and both are high,the catalyst exhibits its maximum activity The mechanism ofcatalytic hydroformylation has been discussed.
基金This work was supported by the National Natural Science Foundation of China (No. 20272058) and the Program of Science and Technique Plan of Fujian province
文摘A new polymeric cobalt complex [Co(-male)(py)(H2O)]n (male = maleate; py = pyridine) 1 was prepared by cobalt chloride hexahydrate with disodium maleate and pyridine in an alcohol-aqueous solution. Single-crystal X-ray analysis has revealed that 1 crystallizes in the orthor- hombic system, space group Pnma with a = 18.001(1), b = 7.6001(6), c = 7.4731(6) ? V = 1022.4(1) 3, Z = 4, C9H9CoNO5, Mr = 270.10, Dc = 1.755 g/cm3, F(000) = 548, m(MoK? = 1.683 mm-1, S = 1.002, the final R = 0.0280 and wR = 0.0746 for 883 observed reflections with I > 2s(I). The structure analysis shows an approximate octahedral coordination environment of metal center. The Co(II) ions are bridged by maleic anions in a rare tetradentate coordination fashion with a syn-anti coplanar con- formation of the carboxyl group, forming a two-dimensional corrugated 2-D structure which is further attached into a three-dimensional framework via non-classical CH…O interactions between adjacent layers.
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.