Binuclear complexes have attracted extensive attention in fields such as catalysis because of their likely bimetallic synergistic effect;however,the mechanism and factors influencing this synergism remain unclear.In t...Binuclear complexes have attracted extensive attention in fields such as catalysis because of their likely bimetallic synergistic effect;however,the mechanism and factors influencing this synergism remain unclear.In this work,six bis-β-ketoimine binuclear titanium complexes4a-4f containing different alkylthio sidearms and configurations were synthesized and characterized by nuclear magnetic resonance hydrogen spectrum(~1H-NMR),nuclear magnetic resonance carbon spectrum(^(13)C-NMR),Fourier transform infrared spectrum(FTIR),and elemental analysis.The intermetallic distances of isomeric complexes 4a,4d,4e and 4f determined through density functional theory(DFT)optimization were in the order 4a<4d<4e<4f and were found to significantly influence the catalytic performance for ethylene(co)polymerization.These complexes could efficiently catalyze ethylene polymerization and ethylene/1-hexene or ethylene/1-octene copolymerization with high activity to produce highmolecular-weight ethylene homo-and co-polymers.Among the three binuclear titanium complexes 4a-4c with similar structures but different lengths of alkylthio sidearms,complex 4a,which contained the shortest methylthio sidearm,exhibited the highest activity for ethylene polymerization and copolymerization with 1-hexene or 1-octene.Additionally,for ethylene/1-hexene or ethylene/1-octene copolymerization,it showed the highest comonomer incorporation compared with propylthio(4b)and octylthio(4c)derivatives because of the smaller steric hindrance of the methyl group in 4a and the more open coordination space for vinyl monomers.Furthermore,among the isomeric complexes 4a,4d,4e and4f,complex 4a with the shortest bimetallic distance also exhibited the highest activity towards ethylene(co)polymerization,and the highest 1-hexene or 1-octene incorporation in comparison with its regioisomeric counterparts 4d,4e and p-phenyl-bridged analog 4f,owing to a more appropriate bimetallic distance that is conducive to a synergistic effect.展开更多
Photoredox-mediated reversible-deactivation radical polymerization(RDRP)is an effective approach to synthesize polymers with defined composition and architecture.Current photoinduced RDRP primarily depends on outer-sp...Photoredox-mediated reversible-deactivation radical polymerization(RDRP)is an effective approach to synthesize polymers with defined composition and architecture.Current photoinduced RDRP primarily depends on outer-sphere electron transfer or homolysis mechanisms.Herein,we describe an example of iodine-mediated RDRP facilitated by photoinduced charge transfer complex(CTC)catalysis.The approach uses cheap and easily accessible N^(-)heterocyclic nitrenium salt(NHN^(+)...I^(-))as the photoactive CTC.Upon the irradiation of visible light,NHN^(+)...I^(-)undergoes single electron transfer to generate NHN·and I·radicals.The NHN·radical activates dormant Pn-I polymers via inner-sphere single electron transfer,leading to the propagating Pn·radical for chain growth and the I^(-)anion for recovering the CTC,and the I·radical deactivates the polymerization via coupling with Pn·.展开更多
The article describes ethylene polymerization reactions with transition metal catalysts based on complexes of CoCl_(2) and FeCl_(2) with an N,N,N-tridentate ligand 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine. Th...The article describes ethylene polymerization reactions with transition metal catalysts based on complexes of CoCl_(2) and FeCl_(2) with an N,N,N-tridentate ligand 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine. The complexes are converted into polymerization catalysts by reacting them either with polymethylalumoxane (MAO) or with a combination of Al(C2H5)2Cl and Mg(C4H9)2 at an [Al]:[Mg] ratio of ~3. Both MAO-activated complexes readily polymerize ethylene at 35 ℃ with the formation of linear, low molecular weight polymers with a narrow molecular weight distribution. The same complexes, when activated with the Al(C2H5)2Cl-Mg(C4H9)2 combination, form multi-center catalysts and generate polyethylenes with a broad molecular weight distribution.展开更多
The effects of the calorimetric buffer solutions were investigated while the two colorimetric reactions of AI-ferron complex and Fe-ferron complex occurred individually, and the effects of the testing wavelength and t...The effects of the calorimetric buffer solutions were investigated while the two colorimetric reactions of AI-ferron complex and Fe-ferron complex occurred individually, and the effects of the testing wavelength and the pH of the solutions were also investigated. A timed complexatian colorimetric analysis method of Al-Fe-ferron in view of the total concentration of {AI + Fe} was then established to determine the species distribution of polymeric Al-Fe. The testing wavelength was recommended at 362 net and the testing pH value was 5. With a comparison of the ratios of n(Al)/n(Fe), the standard adsorption curves of the polymeric Al-Fe solutions were derived from the experimental results. Furthermore, the solutions' composition were carious in both the molar n(Al)/n(Fe) ratios, i.e. 0/0, 5/5, 9/1 and 0/10, and the concentrations associated with the total ( Al + Fe which ranged from 10(-5) to 10(-4) mol/L..展开更多
A new coordination polymer, [Mn（L）（1,4-bdc）] （L = 11-fluoro-dipyrido[3,2- a：2＂,3 ＂- c]phenazine, 1,4-bdc - benzene-1,4-dicarboxylate）, has been synthesized through the hydrothermal method and characterized by...A new coordination polymer, [Mn（L）（1,4-bdc）] （L = 11-fluoro-dipyrido[3,2- a：2＂,3 ＂- c]phenazine, 1,4-bdc - benzene-1,4-dicarboxylate）, has been synthesized through the hydrothermal method and characterized by elemental analysis, IR and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 9.7544（9）, b = 10.8254（10）, c = 11.5288（10） A, a = 114.1300（10）, β = 96.6110（10）, y = 105.0390（10）°, V= 1038.62（16）/k3, Z= 2, C26H13FMnN404, Mr = 519.34, Dc = 1.661 g/cm3, F（000） = 526, ,u（MoKa） = 0.691 mm^-, R = 0.0405 and wR = 0.0977. The 1,4-bdc dianions link the neighboring Mn（II） atoms to yield a two-dimensional layer structure. The L ligands are attached on both sides of the layer. The π-π interactions between the L ligands of neighboring layers result in a three-dimensional supramolecular architecture.展开更多
A new 2D coordination polymer, {[Cd5(BTC)2(L)4(H2O)2]n·2H2O}n(1, H3BTC = 1,3,5-benzenetricarboxylic acid, HL = 3-(2-pyridyl)pyrazole) was synthesized under hydrothermal conditions and characterized by single-crys...A new 2D coordination polymer, {[Cd5(BTC)2(L)4(H2O)2]n·2H2O}n(1, H3BTC = 1,3,5-benzenetricarboxylic acid, HL = 3-(2-pyridyl)pyrazole) was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, powder XRD, IR, TGA, fluorescence spectrum and elemental analysis techniques. Complex 1 belongs to the monoclinic system, P21/c space group, with a = 8.8732(4), b = 17.5179(7), c = 17.8123(7) ?, β = 103.1830(10)°, V = 2695.77(19) ?3 and Z = 2. It features a 2D network constructed by BTC and L ligand. In addition, we analyzed Natural Bond Orbital(NBO) by using the PBE0/LANL2DZ method built in Gaussian 09 Program. The calculation results indicated obvious covalent interactions between the coordinated atoms and Cd(Ⅱ) ion.展开更多
The title complex [Fe（L-trp）2（HL-trp）2]n （L-trp = L-tryptohan or 2-amino-3-（1H -indol-3-yl）-propanoic acid） has been formed by a hydrothermal method involving hexaaquacobaltous perchlorate and L-tryptophan. Th...The title complex [Fe（L-trp）2（HL-trp）2]n （L-trp = L-tryptohan or 2-amino-3-（1H -indol-3-yl）-propanoic acid） has been formed by a hydrothermal method involving hexaaquacobaltous perchlorate and L-tryptophan. The product was characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P211c, with a = 19.828（3）, b = 5.4233（14）, c = 9.2796（16） A, β= 97.691（2）°, V = 988.9（3） A3, Z = 2, Mr = 462.29, Dx = 1.553 g/cm3, F（000） = 480,/a = 0.802 mm^-1, the final R = 0.0399 and wR = 0.0930 for 1738 observed reflections with I 〉 2σ（/）. The structural analysis shows that the complex assumes a two-dimensional double chain plane structure.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
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
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
A novel two-dimensional lead（II） coordination polymer 1, [C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand（5-chloro-quinolin-8-yloxy）acetic acid（HL） with PbCl2, and its structur...A novel two-dimensional lead（II） coordination polymer 1, [C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand（5-chloro-quinolin-8-yloxy）acetic acid（HL） with PbCl2, and its structure was characterized by IR, elemental analysis, TG-DTA and single-crystal X-ray diffraction analysis. The crystal is of monoclinic system, space group P21/c with a = 16.7603（7）, b = 8.6907（4）, c = 8.4745（3）A, β = 101.1110（11）°, C11H7Cl2NO3 Pb, Mr = 479.27, V = 1211.25（9）A3, Z = 4, Dc = 2.628 g/cm^3, F（000） = 880, μ = 14.367 mm^-1, R = 0.0173 and wR = 0.0508. The asymmetric unit contains one lead（II） cation, one（5-chloro-quinolin-8-yloxy）acetate（L） ligand and a chloride ion. The PbII center is hepta-coordinated in a distorted pentagonal bipyramidal geometry. The coordination sphere of the Pb atom is completed by two oxygen atoms and one nitrogen atom of the same L ligand, two bridging chloride ions and two bridging oxygen atoms of two adjacent L ligands. Two PbII centers are linked by the two L ligands to form a C2-symmetric dimer unit with a planar [Pb2O2] ring. Each dimer unit acts as a secondary building unit（SBU） and links adjacent four dimer units by the chloride atoms and oxygen atoms of carboxylate groups of L, forming a two-dimensional array. Such two-dimensional layers are packed through intermolecular C–H…Cl hydrogen bonds into a three-dimensional supramolecular structure. When the dimer unit is viewed as a 4-connected node, 1 is simplified as a 4-nodal 2-D network with square lattices of the diagonal lengths to be 6.079（1）A. The fluorescence emission peak of complex 1 appears near 407 nm.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
The title complex [NH4]n [WAgS4]n crystallizes in the tetragonalspace group I4 with crystallographic parameters: a = b = 7. 994 (2 ), c = 5. 855 (2 ):A,V = 373. g(2) A3, Z=2, Dc= 3. 89 g/cm3, F(000) = 392, μ= 19. 27 ...The title complex [NH4]n [WAgS4]n crystallizes in the tetragonalspace group I4 with crystallographic parameters: a = b = 7. 994 (2 ), c = 5. 855 (2 ):A,V = 373. g(2) A3, Z=2, Dc= 3. 89 g/cm3, F(000) = 392, μ= 19. 27 mm-l , A(MoKα) = 0. 71069, Mr = 438. 01, and the convergence factors R = 0. 045, Rw =0. 055 for 341 observed reflections (I>3σ(I)). The anion structure can be viewed as apolymeric single chain consisting of unlimited extended rhombic fragruents of -AgS2W-which are alternately perpendicular to each other. Additionally, influence of di- and tri-valent complex cations on the assembIy of WS2-4 and Ag+ is briefly discussed.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
Four new polymeric oxa-thiacrown ethers were prepared by the intramolecular cy-clization of poly (2-chloroethylglycidyl ether) with dimercaptans, which is the most convenient method for synthesizing poly(thiacrownethe...Four new polymeric oxa-thiacrown ethers were prepared by the intramolecular cy-clization of poly (2-chloroethylglycidyl ether) with dimercaptans, which is the most convenient method for synthesizing poly(thiacrownether)s. The poly(thiacrownether)s exhibited excellent complexation properties for noble metal ions such as Au ( Ⅲ ) , Pd ( Ⅱ ) and Ag( Ⅰ ) , except Pt( Ⅳ ). In addition, the XPS of polymeric thiacrown ether (PC3) and its complexes of Au( Ⅲ ) and Pd( Ⅱ ) were determined.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
Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfull...Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.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
基金financially supported by the National Natural Science Foundation of China(No.21172269)the Fundamental Research Funds for the Central Universities,SouthCentral Minzu University(No.CZH24005)。
文摘Binuclear complexes have attracted extensive attention in fields such as catalysis because of their likely bimetallic synergistic effect;however,the mechanism and factors influencing this synergism remain unclear.In this work,six bis-β-ketoimine binuclear titanium complexes4a-4f containing different alkylthio sidearms and configurations were synthesized and characterized by nuclear magnetic resonance hydrogen spectrum(~1H-NMR),nuclear magnetic resonance carbon spectrum(^(13)C-NMR),Fourier transform infrared spectrum(FTIR),and elemental analysis.The intermetallic distances of isomeric complexes 4a,4d,4e and 4f determined through density functional theory(DFT)optimization were in the order 4a<4d<4e<4f and were found to significantly influence the catalytic performance for ethylene(co)polymerization.These complexes could efficiently catalyze ethylene polymerization and ethylene/1-hexene or ethylene/1-octene copolymerization with high activity to produce highmolecular-weight ethylene homo-and co-polymers.Among the three binuclear titanium complexes 4a-4c with similar structures but different lengths of alkylthio sidearms,complex 4a,which contained the shortest methylthio sidearm,exhibited the highest activity for ethylene polymerization and copolymerization with 1-hexene or 1-octene.Additionally,for ethylene/1-hexene or ethylene/1-octene copolymerization,it showed the highest comonomer incorporation compared with propylthio(4b)and octylthio(4c)derivatives because of the smaller steric hindrance of the methyl group in 4a and the more open coordination space for vinyl monomers.Furthermore,among the isomeric complexes 4a,4d,4e and4f,complex 4a with the shortest bimetallic distance also exhibited the highest activity towards ethylene(co)polymerization,and the highest 1-hexene or 1-octene incorporation in comparison with its regioisomeric counterparts 4d,4e and p-phenyl-bridged analog 4f,owing to a more appropriate bimetallic distance that is conducive to a synergistic effect.
基金Supported by the National Natural Science Foundation of China(Nos.21773240 and 22173103)the University of the Chinese Academy of Sciences and Beijing National Laboratory for Molecular Sciences(No.BNLMS2023014)。
文摘Photoredox-mediated reversible-deactivation radical polymerization(RDRP)is an effective approach to synthesize polymers with defined composition and architecture.Current photoinduced RDRP primarily depends on outer-sphere electron transfer or homolysis mechanisms.Herein,we describe an example of iodine-mediated RDRP facilitated by photoinduced charge transfer complex(CTC)catalysis.The approach uses cheap and easily accessible N^(-)heterocyclic nitrenium salt(NHN^(+)...I^(-))as the photoactive CTC.Upon the irradiation of visible light,NHN^(+)...I^(-)undergoes single electron transfer to generate NHN·and I·radicals.The NHN·radical activates dormant Pn-I polymers via inner-sphere single electron transfer,leading to the propagating Pn·radical for chain growth and the I^(-)anion for recovering the CTC,and the I·radical deactivates the polymerization via coupling with Pn·.
基金carried out according to the program of Fundamental Scientific Research of the Russian Federation
文摘The article describes ethylene polymerization reactions with transition metal catalysts based on complexes of CoCl_(2) and FeCl_(2) with an N,N,N-tridentate ligand 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine. The complexes are converted into polymerization catalysts by reacting them either with polymethylalumoxane (MAO) or with a combination of Al(C2H5)2Cl and Mg(C4H9)2 at an [Al]:[Mg] ratio of ~3. Both MAO-activated complexes readily polymerize ethylene at 35 ℃ with the formation of linear, low molecular weight polymers with a narrow molecular weight distribution. The same complexes, when activated with the Al(C2H5)2Cl-Mg(C4H9)2 combination, form multi-center catalysts and generate polyethylenes with a broad molecular weight distribution.
基金TheNationalNaturalScienceFoundationofChina (No .2 96 770 0 4)
文摘The effects of the calorimetric buffer solutions were investigated while the two colorimetric reactions of AI-ferron complex and Fe-ferron complex occurred individually, and the effects of the testing wavelength and the pH of the solutions were also investigated. A timed complexatian colorimetric analysis method of Al-Fe-ferron in view of the total concentration of {AI + Fe} was then established to determine the species distribution of polymeric Al-Fe. The testing wavelength was recommended at 362 net and the testing pH value was 5. With a comparison of the ratios of n(Al)/n(Fe), the standard adsorption curves of the polymeric Al-Fe solutions were derived from the experimental results. Furthermore, the solutions' composition were carious in both the molar n(Al)/n(Fe) ratios, i.e. 0/0, 5/5, 9/1 and 0/10, and the concentrations associated with the total ( Al + Fe which ranged from 10(-5) to 10(-4) mol/L..
基金Supported by the Institute Foundation of Siping City (No.2009011)
文摘A new coordination polymer, [Mn（L）（1,4-bdc）] （L = 11-fluoro-dipyrido[3,2- a：2＂,3 ＂- c]phenazine, 1,4-bdc - benzene-1,4-dicarboxylate）, has been synthesized through the hydrothermal method and characterized by elemental analysis, IR and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 9.7544（9）, b = 10.8254（10）, c = 11.5288（10） A, a = 114.1300（10）, β = 96.6110（10）, y = 105.0390（10）°, V= 1038.62（16）/k3, Z= 2, C26H13FMnN404, Mr = 519.34, Dc = 1.661 g/cm3, F（000） = 526, ,u（MoKa） = 0.691 mm^-, R = 0.0405 and wR = 0.0977. The 1,4-bdc dianions link the neighboring Mn（II） atoms to yield a two-dimensional layer structure. The L ligands are attached on both sides of the layer. The π-π interactions between the L ligands of neighboring layers result in a three-dimensional supramolecular architecture.
基金supported by the Science and Technology development plan of Jilin Province(2015052006JH)
文摘A new 2D coordination polymer, {[Cd5(BTC)2(L)4(H2O)2]n·2H2O}n(1, H3BTC = 1,3,5-benzenetricarboxylic acid, HL = 3-(2-pyridyl)pyrazole) was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, powder XRD, IR, TGA, fluorescence spectrum and elemental analysis techniques. Complex 1 belongs to the monoclinic system, P21/c space group, with a = 8.8732(4), b = 17.5179(7), c = 17.8123(7) ?, β = 103.1830(10)°, V = 2695.77(19) ?3 and Z = 2. It features a 2D network constructed by BTC and L ligand. In addition, we analyzed Natural Bond Orbital(NBO) by using the PBE0/LANL2DZ method built in Gaussian 09 Program. The calculation results indicated obvious covalent interactions between the coordinated atoms and Cd(Ⅱ) ion.
基金Supported by the foundation of the Science Committee of Jiangsu Province (No. BK2005045)the Key Marine Biotechnology Laboratory of Jiangsu Province (No. 2005HS010)
文摘The title complex [Fe（L-trp）2（HL-trp）2]n （L-trp = L-tryptohan or 2-amino-3-（1H -indol-3-yl）-propanoic acid） has been formed by a hydrothermal method involving hexaaquacobaltous perchlorate and L-tryptophan. The product was characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P211c, with a = 19.828（3）, b = 5.4233（14）, c = 9.2796（16） A, β= 97.691（2）°, V = 988.9（3） A3, Z = 2, Mr = 462.29, Dx = 1.553 g/cm3, F（000） = 480,/a = 0.802 mm^-1, the final R = 0.0399 and wR = 0.0930 for 1738 observed reflections with I 〉 2σ（/）. The structural analysis shows that the complex assumes a two-dimensional double chain plane structure.
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 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Supported by Key Laboratory of Organic Synthesis of Jiangsu Province(KJS1308)
文摘A novel two-dimensional lead（II） coordination polymer 1, [C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand（5-chloro-quinolin-8-yloxy）acetic acid（HL） with PbCl2, and its structure was characterized by IR, elemental analysis, TG-DTA and single-crystal X-ray diffraction analysis. The crystal is of monoclinic system, space group P21/c with a = 16.7603（7）, b = 8.6907（4）, c = 8.4745（3）A, β = 101.1110（11）°, C11H7Cl2NO3 Pb, Mr = 479.27, V = 1211.25（9）A3, Z = 4, Dc = 2.628 g/cm^3, F（000） = 880, μ = 14.367 mm^-1, R = 0.0173 and wR = 0.0508. The asymmetric unit contains one lead（II） cation, one（5-chloro-quinolin-8-yloxy）acetate（L） ligand and a chloride ion. The PbII center is hepta-coordinated in a distorted pentagonal bipyramidal geometry. The coordination sphere of the Pb atom is completed by two oxygen atoms and one nitrogen atom of the same L ligand, two bridging chloride ions and two bridging oxygen atoms of two adjacent L ligands. Two PbII centers are linked by the two L ligands to form a C2-symmetric dimer unit with a planar [Pb2O2] ring. Each dimer unit acts as a secondary building unit（SBU） and links adjacent four dimer units by the chloride atoms and oxygen atoms of carboxylate groups of L, forming a two-dimensional array. Such two-dimensional layers are packed through intermolecular C–H…Cl hydrogen bonds into a three-dimensional supramolecular structure. When the dimer unit is viewed as a 4-connected node, 1 is simplified as a 4-nodal 2-D network with square lattices of the diagonal lengths to be 6.079（1）A. The fluorescence emission peak of complex 1 appears near 407 nm.
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The title complex [NH4]n [WAgS4]n crystallizes in the tetragonalspace group I4 with crystallographic parameters: a = b = 7. 994 (2 ), c = 5. 855 (2 ):A,V = 373. g(2) A3, Z=2, Dc= 3. 89 g/cm3, F(000) = 392, μ= 19. 27 mm-l , A(MoKα) = 0. 71069, Mr = 438. 01, and the convergence factors R = 0. 045, Rw =0. 055 for 341 observed reflections (I>3σ(I)). The anion structure can be viewed as apolymeric single chain consisting of unlimited extended rhombic fragruents of -AgS2W-which are alternately perpendicular to each other. Additionally, influence of di- and tri-valent complex cations on the assembIy of WS2-4 and Ag+ is briefly discussed.
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.
文摘Four new polymeric oxa-thiacrown ethers were prepared by the intramolecular cy-clization of poly (2-chloroethylglycidyl ether) with dimercaptans, which is the most convenient method for synthesizing poly(thiacrownether)s. The poly(thiacrownether)s exhibited excellent complexation properties for noble metal ions such as Au ( Ⅲ ) , Pd ( Ⅱ ) and Ag( Ⅰ ) , except Pt( Ⅳ ). In addition, the XPS of polymeric thiacrown ether (PC3) and its complexes of Au( Ⅲ ) and Pd( Ⅱ ) were determined.
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.
文摘Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.
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.
