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
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
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
Polymeric cerium nitrate complex with 1,4 bis(phenylsulfinyl)butane (bphsb) [Ce(bphsb) 2(NO 3) 3] n (1) was synthesized and characterized. The crystal structure of the complex indicated that the ligand bphsb ...Polymeric cerium nitrate complex with 1,4 bis(phenylsulfinyl)butane (bphsb) [Ce(bphsb) 2(NO 3) 3] n (1) was synthesized and characterized. The crystal structure of the complex indicated that the ligand bphsb and cerium(Ⅲ) ion form a polymeric double bridge chain complex involving 18 membered macrometallocycles. Each cerium ion is coordinated by ten O atoms in a distorted 4,4 bicapped square antiprism. In the complex the disulfoxide ligand acts as bis monodentate O ligand bridging metal centers.展开更多
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 single crystals of the title compound were obtained from a reaction of MnCO3, benzenetetracarboxylic acid (H4BTC) and imidazole in an aqueous solution. The crystal of Mn(II) complex (C28H34Mn2N12O124H2O, Mr = 912....The single crystals of the title compound were obtained from a reaction of MnCO3, benzenetetracarboxylic acid (H4BTC) and imidazole in an aqueous solution. The crystal of Mn(II) complex (C28H34Mn2N12O124H2O, Mr = 912.62) belongs to tricli nic, space group P?with a = 10.036(1), b = 10.650(1), c = 11.102(1) , a = 114.72(2), b = 95.75(1), g = 108.46(2)o, V = 984.2(2) 3, Z = 1, Dc = 1.540 g/cm3, F(000) = 472, m(MoKa) = 0.726 mm-1, R = 0.0409 and wR = 0.1166 for 3909 observed reflections (I > 2s(I)). The crystal consists of the polymeric Mn(II) complex anions and discrete Mn(II) complex cations, both with normal octahedral coordination geometry. Each BTC bridges two Mn(II) atoms to form the anionic polymeric chain, and the cations distribute be- tween the chains and link them through both classic and weak CH…O H-bonding.展开更多
It is a long-term pursuit,and also,a challenge to significantly improve the mechanical strength of thermoplastic polymers using readily dispersed polymers as nanofillers.In this study,we demonstrated that in situ form...It is a long-term pursuit,and also,a challenge to significantly improve the mechanical strength of thermoplastic polymers using readily dispersed polymers as nanofillers.In this study,we demonstrated that in situ formed carboxylic acid-functionalized poly(aryl ether sulfone)(PAES-COOH)/polyvinylpyrrolidone(PVPON)complex nanoparticles can significantly enhance the mechanical strength of PAES-COOH by mixing PAES-COOH with a small fraction of PVPON.The PAES-COOH/PVPON10%composite,which contained∼10 wt%PVPON,exhibited a tensile strength of∼104.8 MPa and Young’s modulus of∼932.2 MPa,which were∼2.0 and∼1.7 times higher than those of the PAES-COOH,respectively.The PAES-COOH/PVPON nanoparticles which were uniformly dispersed in PAES-COOH matrices and had strong hydrogen-bonding interactions with PAES-COOH,served as nanofillers to reinforce the mechanical strength of the PAES-COOH.The PAES-COOH/PVPON_(10%)composites possessed excellent solvent-assisted healability,and the fractured composites could be healed to restore their original mechanical strength.Meanwhile,the PAES-COOH/PVPON_(10%)composites could be recycled multiple times,and yet retained their shape integration and their original mechanical strength.展开更多
In this study,the electronic transition properties and structural analysis of the metal complexes(Ni(Ⅱ),Co(Ⅱ),Cu(Ⅱ)and Mn(Ⅱ))of three different polymer ligands were performed by using XRF and X-ray diffraction(XRD...In this study,the electronic transition properties and structural analysis of the metal complexes(Ni(Ⅱ),Co(Ⅱ),Cu(Ⅱ)and Mn(Ⅱ))of three different polymer ligands were performed by using XRF and X-ray diffraction(XRD)techniques,respectively.The structural analysis of the polymers and their complexes were performed by XRD technique and some of the polymers were found to be in the face-centred cubic(fcc)structure.In addition,the values of the present K X-ray intensity ratios are significantly greater than the values reported in literature.展开更多
ESR and IR measurements have been carried out for a copper(Ⅱ)complex of phenolic polymeric crown ether,As a result,the triplet ESR spectrum(S=1)of 3d_z2 ground state copper(Ⅱ)ions was first observed for the powder s...ESR and IR measurements have been carried out for a copper(Ⅱ)complex of phenolic polymeric crown ether,As a result,the triplet ESR spectrum(S=1)of 3d_z2 ground state copper(Ⅱ)ions was first observed for the powder sample.It indicated that there existed intramolecular spin-spin interaction betweeen 3d_Z2 ground state copper(Ⅱ)and copper(Ⅱ)ions.In this binuclear triplet cluster,the axial ligntion of one water molecule in a sandwich position to two adjacent copper(Ⅱ) ions was also confirmed by IR spectra,All things considered,a possible structure for the complex was proposed.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
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
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
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
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 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
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
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.
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Polymeric cerium nitrate complex with 1,4 bis(phenylsulfinyl)butane (bphsb) [Ce(bphsb) 2(NO 3) 3] n (1) was synthesized and characterized. The crystal structure of the complex indicated that the ligand bphsb and cerium(Ⅲ) ion form a polymeric double bridge chain complex involving 18 membered macrometallocycles. Each cerium ion is coordinated by ten O atoms in a distorted 4,4 bicapped square antiprism. In the complex the disulfoxide ligand acts as bis monodentate O ligand bridging metal centers.
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 single crystals of the title compound were obtained from a reaction of MnCO3, benzenetetracarboxylic acid (H4BTC) and imidazole in an aqueous solution. The crystal of Mn(II) complex (C28H34Mn2N12O124H2O, Mr = 912.62) belongs to tricli nic, space group P?with a = 10.036(1), b = 10.650(1), c = 11.102(1) , a = 114.72(2), b = 95.75(1), g = 108.46(2)o, V = 984.2(2) 3, Z = 1, Dc = 1.540 g/cm3, F(000) = 472, m(MoKa) = 0.726 mm-1, R = 0.0409 and wR = 0.1166 for 3909 observed reflections (I > 2s(I)). The crystal consists of the polymeric Mn(II) complex anions and discrete Mn(II) complex cations, both with normal octahedral coordination geometry. Each BTC bridges two Mn(II) atoms to form the anionic polymeric chain, and the cations distribute be- tween the chains and link them through both classic and weak CH…O H-bonding.
基金This work was supported by the National Natural Science Foundation of China(NSFC grant 20935004 and 21774049).
文摘It is a long-term pursuit,and also,a challenge to significantly improve the mechanical strength of thermoplastic polymers using readily dispersed polymers as nanofillers.In this study,we demonstrated that in situ formed carboxylic acid-functionalized poly(aryl ether sulfone)(PAES-COOH)/polyvinylpyrrolidone(PVPON)complex nanoparticles can significantly enhance the mechanical strength of PAES-COOH by mixing PAES-COOH with a small fraction of PVPON.The PAES-COOH/PVPON10%composite,which contained∼10 wt%PVPON,exhibited a tensile strength of∼104.8 MPa and Young’s modulus of∼932.2 MPa,which were∼2.0 and∼1.7 times higher than those of the PAES-COOH,respectively.The PAES-COOH/PVPON nanoparticles which were uniformly dispersed in PAES-COOH matrices and had strong hydrogen-bonding interactions with PAES-COOH,served as nanofillers to reinforce the mechanical strength of the PAES-COOH.The PAES-COOH/PVPON_(10%)composites possessed excellent solvent-assisted healability,and the fractured composites could be healed to restore their original mechanical strength.Meanwhile,the PAES-COOH/PVPON_(10%)composites could be recycled multiple times,and yet retained their shape integration and their original mechanical strength.
基金Scientific Research Fund of Kahramanmaras Sutcu Imam University,Turkey(2012/3-7YLS)
文摘In this study,the electronic transition properties and structural analysis of the metal complexes(Ni(Ⅱ),Co(Ⅱ),Cu(Ⅱ)and Mn(Ⅱ))of three different polymer ligands were performed by using XRF and X-ray diffraction(XRD)techniques,respectively.The structural analysis of the polymers and their complexes were performed by XRD technique and some of the polymers were found to be in the face-centred cubic(fcc)structure.In addition,the values of the present K X-ray intensity ratios are significantly greater than the values reported in literature.
文摘ESR and IR measurements have been carried out for a copper(Ⅱ)complex of phenolic polymeric crown ether,As a result,the triplet ESR spectrum(S=1)of 3d_z2 ground state copper(Ⅱ)ions was first observed for the powder sample.It indicated that there existed intramolecular spin-spin interaction betweeen 3d_Z2 ground state copper(Ⅱ)and copper(Ⅱ)ions.In this binuclear triplet cluster,the axial ligntion of one water molecule in a sandwich position to two adjacent copper(Ⅱ) ions was also confirmed by IR spectra,All things considered,a possible structure for the complex was proposed.
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.
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.
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.
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.